SOLVENT EXTRACTION

State and explain Nerst Distribution Law

The Nernst Distribution Law, also known as the Partition Law, states that when a solute is
distributed between two immiscible solvents at equilibrium, the ratio of the concentrations of the
solute in each solvent remains constant, provided the temperature remains constant and the
solute does not undergo any association or dissociation in either solvent.

Mathematically, the law is expressed as

𝐶1
𝐾𝐷 =
𝐶2
Where:

• 𝐶1 is the concentration of the solute in solvent 1 (usually the organic solvent).

• 𝐶2 is the concentration of the solute in solvent 2 (usually the aqueous solvent).
• 𝐾𝐷 is the distribution coefficient or partition coefficient.

Explanation of the Law:

When a solute is introduced to two immiscible solvents (e.g., water and an organic solvent like
chloroform), it distributes itself between the two solvents in such a way that the ratio of its
concentrations in the two phases is constant at equilibrium. This is only true if the solute remains in
the same molecular form in both phases, i.e., it does not dissociate or associate.

The value of 𝐾𝐷 depends on the nature of the solute and the solvents. It reflects the relative
solubility of the solute in the two solvents. A large value of 𝐾𝐷 means the solute prefers the organic
phase, while a small 𝐾𝐷 means it prefers the aqueous phase.

Applications

i. The distribution law is successfully applied in the study of dissociation or association of a

solute in a solvent
ii. It can be used to determine the equilibrium constant for a complex reaction
iii. It can be used to determine the solubility of a solute
iv. It finds numerous applications in the process of extraction of a solute from solvent in both
lab and in industry such as pharmaceuticals
v. It can be used for determining the test of Bromide and Iodide

Limitations / Factors causing deviations from the law

• If the solute forms compunds with one of the solvent the law would remain valid except that
the numerical value of the partition coefficient changes. Thus the chemical reaction of the
solute does not have any effect on this law.

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 • If the solute undergoes association in one of the solvent but remains unchanged in the other
then the usual form of this law is not applicable. In that case, the law becomes,

• If the solute undergoes dissociation in one of the solvent but remains unchanged in the other
then the usual form of this law is not applicable. In that case, the law becomes,

• If the solute undergoes association in one of the solvent and dissociation in other, then the
law is modified as

• The solute must reach equilibrium between the two phases.

• The temperature must remains constant.
• The two solvent must be mutually immiscible
• The amount of solute should be small , i.e. the solution should be dilute.

What is Distribution Ratio?

The distribution ratio (D) is a measure of how a solute distributes itself between two immiscible
phases, usually an organic solvent and an aqueous solution. It is defined as the ratio of the total
amount of solute in one phase to the total amount in the other phase at equilibrium, taking into
account all forms of the solute present (free, bound, or in complex forms).

It can be expressed as,

𝑇𝑜𝑡𝑎𝑙 𝑐𝑜𝑛𝑐. 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖𝑛 𝑝ℎ𝑎𝑠𝑒 𝐼

𝐷=
𝑇𝑜𝑡𝑎𝑙 𝑐𝑜𝑛𝑐. 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖𝑛 𝑝ℎ𝑎𝑠𝑒 𝐼𝐼

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Principle of Solvent Extraction
An important application of the distribution law is in the extraction of a solute from a solvent by
another solvent. If the solubilities of a solute in two mutually immiscible liquids are different, then
on shaking the solution of the solute in solvent I with solvent II, a considerable amount of solute will
pass into the solvent II. If now solvent II is separated from solvent I, a part of solute which has been
extracted away from solvent I may be recorded. A second part of the solute may be extracted from
solvent I by shaking with a fresh portion of solvent II and separated. This process of separation is
called solvent extraction.

According to the Gibbs Phase Rule, F+P=C+2

Here, Number of phases, P=2 (aqueous and organic)
Number of component, C=1 (solute)
Hence at constant temperature and pressure, the phase rule becomes:
F+2=1+2
F=1
If C1 and C2 are the concentrations of the solute in phase I and II in equilibrium, the according to the
Nerst Distribution law,
𝐶1
𝐾𝐷 =
𝐶2
Where, 𝐾𝐷 is the distribution coefficient. This is independent of the total solute conc. in either of the
solvent. In this expression we have not considered the activity coefficient for the species in two
phases. We therefore, use the term distribution ratio, D, in order to account for the total conc. of the
species in two phases. The distribution ratio is defined as
𝑇𝑜𝑡𝑎𝑙 𝑐𝑜𝑛𝑐. 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖𝑛 𝑝ℎ𝑎𝑠𝑒 𝐼
𝐷=
𝑇𝑜𝑡𝑎𝑙 𝑐𝑜𝑛𝑐. 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖𝑛 𝑝ℎ𝑎𝑠𝑒 𝐼𝐼
If there is no association, dissociation or polymerization of the solute in the two phases, the D=K D

(Derive the Equation for Single Step Extraction and Multiple Step Extraction here)

Derive Relationship Between D, KD, Ka and [H+]

Derive Relationship Between D, KD
Effect of pH on Solvent Extraction

The distribution coefficient D is used in place of the partition coefficient KD when dealing with a
species that has more than one chemical form, such as HA and A-.

The distribution ratio (D) is defined as the ratio of the concentration of the compound in the
organic phase to its total concentration (both ionized and non-ionized forms) in the aqueous phase.

Benzoic acid dissociates in aqueous media as follows:

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where

[HBz]o is the concentration of the neutral (molecular) form of the substance in the organic phase

[HBz]a is the concentration of the neutral (molecular) form in the aqueous phase.

[Bz−]a is the concentration of the ionized form in the aqueous phase.

In aqueous medium, benzoic acid (HBz) dissociates into hydrogen ions (H⁺) and benzoate ions
(Bz⁻) according to the following equilibrium:

Here, Ka is the dissociation constant.

Rearranging this to find [Bz−]:

The distribution coefficient (KD) relates the concentration of the molecular form of benzoic acid in
the organic phase to its concentration in the aqueous phase:

Therefore:

[𝐻𝐵𝑧]𝑜 = 𝐾𝐷 [𝐻𝐵𝑧]𝑎 (equation II)

Now, substituting the values of [Bz−] from Equation I and [HBz]a from Equation II into the
expression for the distribution ratio (D);

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This derivation illustrates how the distribution ratio of benzoic acid between two phases is
influenced by both the pH of the aqueous phase (via the H⁺ concentration) and the acid
dissociation constant (Ka) of benzoic acid. The distribution ratio reflects how much of the acid is
present in its molecular form versus its ionized form in each phase.

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Relationship Between D, KD, and Ka:
𝐾𝐷
𝐷=
𝐾
1 + 𝑎+
[𝐻 ]
𝑲
If Ka ≪ [H+]a , the term [𝑯+𝒂 ] approaches zero.

• Conclusion: The solute will primarily exist in the organic phase (non-ionized form),
as there is little dissociation.
• Reason: In this case, the solute does not dissociate significantly, so it remains in its
neutral, non-ionized form, which is more soluble in the organic phase.
𝑲𝑫 [𝑯+ ]
If Ka ≫ [H+]a , the distribution ratio (D) becomes approximately 𝑲𝒂

• Conclusion: The solute will primarily exist in the aqueous phase (ionized form), as
dissociation is favored.
• Reason: In this case, the solute ionizes significantly due to the higher K a , so it
becomes more hydrophilic (soluble in the aqueous phase).

Effect of [𝑯+ ] on Distribution:

• When [H+] concentration increases: dissociation of the solute decreases (fewer

ions are formed). The solute will predominantly exist in its non-ionized form, and it
will distribute more into the organic phase.
• When [H+] concentration decreases(lower pH): the solute dissociates more,
producing more ions. The solute will predominantly exist in its ionized form,
distributing more into the aqueous phase.

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% Extraction Efficiency:
Extraction efficiency is the ratio of the amount of analyte extracted to the amount of
analyte present in the original sample. It reflects how well the extraction method can
recover the analyte from the matrix.
It is the percentage of a solute in a solvent that has been extracted by another solvent.
𝑊𝑜
%𝐸 = × 100%
𝑊𝑜 + 𝑊𝑎
Where, 𝑊𝑜 is the amount of solute in organic solvent

𝑊𝑎 is the amount of solute in aqueous solvent

We know that, W=SV

Hence,
𝑆𝑜 𝑉𝑜
%𝐸 = × 100%
𝑆𝑜 𝑉𝑜 + 𝑆𝑎 𝑉𝑎
Dividing by 𝑆𝑎 𝑉𝑜 , we get
𝑆𝑜
𝑆𝑎
%𝐸 = × 100%
𝑆𝑜 𝑉𝑎
𝑆𝑎 + 𝑉𝑜
𝑆
As we know, 𝐷 = 𝑆𝑜
𝑎

𝐷
%𝐸 = × 100%
𝑉
𝐷 + 𝑉𝑎
𝑜

If Vo ≫ Va (i.e., the volume of the organic phase is much larger than the aqueous phase),
the extraction efficiency approaches 100%. This is because the majority of the solute will
be transferred into the large volume of the organic phase.

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Problem: From a 20 ml 0.1M aq. Solution of butanoic acid, 10 mL of ether is used to
extract the acid. The aqueous solution retained 0.05 mmol of butanoic acid. Calculate D
and %E.
Solve: 20mL O.1M = 2 mmol
20 ml water contains 0.05 mmol after extraction
So, extracted by ether solvent= (2-0.05)=1.95 mmol
1.95
𝑆𝑜 = = 0.195
10
0.05
𝑆𝑎 = = 0.0025
20

𝑆 0.195
𝐷 = 𝑆𝑜 = 0.0025=78
𝑎

𝐷 78
%𝐸 = × 100% = × 100% = 97.5%
𝑉 20
𝐷 + 𝑉𝑎 78 + 10
𝑜

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Derive an Equation for Single Step Extraction and Multiple Step Extraction
Lets assume, Va mL of solvent ‘a’ contains Wo amount of solute. If Vb mL of solvent ‘b’ is
used to extract solute from solvent ‘a’ then after extraction, solvent ‘a’ contains W1 amount
of solute. Find out W1 and amount of solute extracted by solvent ‘b’ (i.e. Wo-W1). Find out
the eqn for n times of extraction.

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Problem : The distribution co-efficient of an alkaloid between chloroform, and water is
20 in favor of chloroform. Find out the weight of the alkaloid remaining in 100 ml
aqueous solution containing 1 gram when shaken with
(a) 50 ml chloroform and
(b) two successive 25 ml portions.
Also Find out in which case, efficiency is better.

𝑪𝒐𝒏𝒄.𝒊𝒏 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝒂 𝒊𝒏 𝒘𝒂𝒕𝒆𝒓 𝟏

(a) 𝑲𝑫 = = 𝒊𝒏 𝒄𝒉𝒍𝒐𝒓𝒐𝒇𝒐𝒓𝒎 = 𝟐𝟎
𝒄𝒐𝒏𝒄.𝒊𝒏 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝒃

𝑲 𝑫 𝑽𝒂
𝑾𝟏 = 𝑾𝒐 ( )
𝑽𝒃 + 𝑲 𝑫 𝑽𝒂

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 𝟏
× 𝟏𝟎𝟎
𝑾𝟏 = 𝟏 × 𝟐𝟎 = 𝟎. 𝟎𝟗𝒈
𝟏
𝟓𝟎 + 𝟐𝟎 × 𝟏𝟎𝟎

𝒂𝒎𝒐𝒖𝒏𝒕 𝒆𝒙𝒕𝒓𝒂𝒄𝒕𝒆𝒅 𝒃𝒚 𝑪𝒉𝒍𝒐𝒓𝒐𝒇𝒐𝒓𝒎 = 𝟏𝒈 − 𝟎. 𝟎𝟗𝒈 = 𝟎. 𝟗𝟏𝒈

𝒂𝒎𝒐𝒖𝒏𝒕 𝒆𝒙𝒕𝒓𝒂𝒄𝒕𝒆𝒅 𝒃𝒚 𝑪𝒉𝒍𝒐𝒓𝒐𝒇𝒐𝒓𝒎
%𝑬 =
𝒐𝒓𝒊𝒈𝒊𝒏𝒂𝒍 𝒂𝒎𝒐𝒖𝒏𝒕 𝒊𝒏 𝒂𝒒𝒖𝒆𝒐𝒖𝒔 𝒔𝒐𝒍𝒗𝒆𝒏𝒕
𝟎. 𝟗𝟏
%𝑬 = × 𝟏𝟎𝟎 = 𝟗𝟏%
𝟏

(b)
𝒏
𝑲 𝑫 𝑽𝒂
𝑾𝒏 = 𝑾𝒐 ( )
𝑽𝒃 + 𝑲 𝑫 𝑽𝒂

𝟐
𝟏
× 𝟏𝟎𝟎
𝑾𝟐 = 𝟏 × ( 𝟐𝟎 ) = 𝟎. 𝟎𝟐𝟕𝒈
𝟏
𝟐𝟓 + 𝟐𝟎 × 𝟏𝟎𝟎

𝒂𝒎𝒐𝒖𝒏𝒕 𝒆𝒙𝒕𝒓𝒂𝒄𝒕𝒆𝒅 𝒃𝒚 𝑪𝒉𝒍𝒐𝒓𝒐𝒇𝒐𝒓𝒎 = 𝟏𝒈 − 𝟎. 𝟎𝟐𝟕𝒈 = 𝟎. 𝟗𝟕𝟑𝒈

𝟎. 𝟗𝟕𝟑
%𝑬 = × 𝟏𝟎𝟎 = 𝟗𝟕. 𝟑%
𝟏
So extracting 2 times using 25 ml portions gives better efficiency than extracting 1 time
with whole 50 ml of chloroform solution.

Problem: The distribution coefficient of an alkaloid between chloroform and water is 20 in

favor of chloroform. Find out the weights of the alkaloid remaining in 100 mL aqueous
solution containing 2 grams of alkaloid when shaken
(a) first with 40 mL of chloroform and then with 60 mL of chloroform.
Solve:
𝑪𝒐𝒏𝒄.𝒊𝒏 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝒂 𝒊𝒏 𝒘𝒂𝒕𝒆𝒓 𝟏
• Distribution coefficient 𝑲𝑫 = = 𝒊𝒏 𝒄𝒉𝒍𝒐𝒓𝒐𝒇𝒐𝒓𝒎 = 𝟐𝟎
𝒄𝒐𝒏𝒄.𝒊𝒏 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝒃
• Initial amount of alkaloid (W₀) = 2 grams

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 • Volume of aqueous solution (Vₐ) = 100 mL
• Volume of chloroform used in the first extraction (Vb₁) = 40 mL
• Volume of chloroform used in the second extraction (Vb₂) = 60 mL

Weight remaining after first extraction:

𝑲 𝑫 𝑽𝒂 1⁄ × 100
𝑾𝟏 = 𝑾𝒐 ( )=2× 20 = 0.22𝑔
𝑽𝒃𝟏 + 𝑲𝑫 𝑽𝒂 40 + 1⁄20 × 100

Weight remaining after 2nd extraction:

𝑲 𝑫 𝑽𝒂 1⁄ × 100
𝑾𝟐 = 𝑾𝟏 ( ) = 0.22 × 20 = 0.016𝑔
𝑽𝒃𝟐 + 𝑲𝑫 𝑽𝒂 60 + 1⁄20 × 100
• Therefore solute remaining in water after two rounds (40+60 mL) of
extraction=0.016g
• Total extracted=2-0.016=1.984g
𝟏.𝟗𝟖𝟓
• %𝑬 = × 𝟏𝟎𝟎 = 𝟗𝟗. 𝟐%
𝟐

Solvent Extraction Classification

1. Solid Phase Extraction (SPE): Involves passing a liquid sample through a solid absorbent
material (stationary phase). The target analytes are adsorbed onto the solid phase and later
eluted with a suitable solvent.
2. Liquid-Liquid Extraction (LLE): Involves transferring a solute from one liquid phase (usually
aqueous) to another immiscible liquid phase (usually organic), based on solubility
differences.

Different types of extraction process

Liquid-Liquid Extraction (LLE)
Liquid-Liquid Extraction (LLE) is a separation technique where two immiscible liquids are
used to separate compounds based on their solubility. One of the liquids is typically
aqueous (water-based), while the other is organic. The solute (analyte) of interest is
transferred from one liquid phase to the other based on its affinity for the two phases.
The key principle behind liquid-liquid extraction is the distribution of solutes between two
immiscible liquids. This distribution is governed by the solubility of the solute in each
liquid, typically represented by the partition coefficient (KD)

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 𝑪𝒐𝒏𝒄. 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒊𝒏 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝒂
𝑲𝑫 =
𝒄𝒐𝒏𝒄. 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒊𝒏 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝒃
The solute prefers one phase over the other depending on its chemical nature. By selecting
appropriate solvents and controlling conditions such as pH or temperature, the efficiency
of extraction can be maximized.
Steps in Liquid-Liquid Extraction:
1. Mixing: The aqueous and organic phases are mixed, allowing the solute to distribute
between them. The solute moves from the phase in which it is less soluble to the
phase in which it is more soluble.
2. Separation of Phases: After mixing, the two phases are allowed to settle and
separate. The organic phase (which is less dense than water) floats on top, while the
aqueous phase remains at the bottom.
3. Recovery of the Extract: The phase that contains the desired solute is removed. The
solute can then be recovered from this phase through evaporation, precipitation, or
another method.
Factors Affecting LLE:
1. Partition Coefficient (K): A larger partition coefficient means better extraction
efficiency, as the solute is more soluble in the organic phase.
2. Solvent Selection: The organic solvent should have high solubility for the target
compound but should be immiscible with the aqueous phase.
3. pH: pH control can significantly impact the ionization of the solute, which affects its
partitioning behavior.
4. Temperature: Changes in temperature can influence the solubility and distribution
of the solute between the two phases.
Advantages of LLE:
• Selective Separation: Highly selective, especially for solutes with significantly
different solubilities in the two phases.
• Versatile: Can be applied to a wide variety of compounds and mixtures.
• Scalable: Effective on both small laboratory scales and large industrial scales.
Disadvantages of LLE:
• Emulsion Formation: In some cases, emulsions may form between the phases,
making separation difficult.

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 • Solvent Use: Requires significant amounts of organic solvent, which may need to be
recovered or disposed of, raising environmental and cost concerns.
• Limited Efficiency: May require multiple extractions (serial extractions) to achieve
complete separation.
Applications of Liquid-Liquid Extraction:
• Pharmaceuticals: LLE is used to isolate and purify active pharmaceutical
ingredients from raw materials.
• Environmental analysis: For extracting pollutants such as pesticides or organic
compounds from water samples.
• Metallurgy: Used for recovering metal ions from aqueous solutions, often in
hydrometallurgical processes.
• Food industry: For flavor extraction, such as isolating essential oils or active
compounds from plant materials.

Liquid-Solid Extraction
Liquid-Solid Extraction (also known as Solid-Liquid Extraction or Leaching) is a
separation process in which a solvent (liquid) is used to extract a solute from a solid matrix.
The process involves the dissolution of one or more components of a solid into a liquid
solvent.
The principle behind liquid-solid extraction is based on the solubility of the target
substance (solute) in the solvent. The solid matrix contains the desired substance, and
when it is brought into contact with the solvent, the soluble component dissolves into the
liquid phase, leaving the insoluble part (impurities) behind.
Factors Affecting Liquid-Solid Extraction:
1. Solvent Selection: The solvent must be able to dissolve the solute effectively while
leaving other components in the solid matrix. Solvent polarity, volatility, and toxicity
must be considered.
2. Temperature: Higher temperatures often increase the solubility of the solute,
speeding up the extraction process. However, sensitive compounds may degrade at
high temperatures.
3. Surface Area: Finely ground solids have a greater surface area, which enhances the
extraction rate.

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 4. Solvent-to-Solid Ratio: The amount of solvent used compared to the amount of
solid affects the efficiency of extraction. Higher solvent volumes can improve
extraction but increase the cost.
Advantages of Liquid-Solid Extraction:
• Selective Extraction: By choosing the appropriate solvent, it’s possible to
selectively extract specific compounds from a solid matrix.
• Simple Process: Many liquid-solid extraction processes, such as maceration or
percolation, require simple equipment.
• Scalable: Can be scaled from small laboratory operations to large industrial
processes.
Disadvantages of Liquid-Solid Extraction:
• Slow Process: Some extraction methods, such as maceration, can be time-
consuming.
• Incomplete Extraction: In some cases, the solvent may not completely remove the
solute, requiring multiple extractions.
• Solvent Use: Large amounts of solvent may be required, leading to higher costs and
environmental concerns.

Supercritical Fluid Extraction (SFE)

Supercritical Fluid Extraction (SFE) is an advanced extraction technique that utilizes
supercritical fluids to extract specific compounds from a solid or liquid matrix. This method
is particularly useful in cases where traditional extraction techniques, such as liquid-liquid
or solid-liquid extraction, might be less efficient or result in unwanted byproducts.
What is a Supercritical Fluid?
A supercritical fluid is a substance at a temperature and pressure above its critical point,
where it exhibits properties of both a gas and a liquid. In the supercritical state, the fluid
can diffuse through solids like a gas and dissolve materials like a liquid, making it an ideal
solvent for extraction.
The most commonly used supercritical fluid in extraction processes is supercritical
carbon dioxide (CO₂) because it is non-toxic, readily available, inexpensive, and easily
removed from the extracted product by simple depressurization.

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Principle of Supercritical Fluid Extraction:
The principle of SFE is based on the tunable properties of supercritical fluids. By adjusting
the pressure and temperature, the solvent power of the supercritical fluid can be fine-
tuned to selectively extract specific compounds. The solvent properties of a supercritical
fluid depend on its density, which can be manipulated by changing the pressure and
temperature conditions.
• Low density makes the supercritical fluid behave more like a gas, which is good for
extracting volatile, low-molecular-weight compounds.
• High density increases the solvent power, making it act like a liquid capable of
dissolving larger, non-volatile compounds.
Advantages of Supercritical Fluid Extraction:
1. Selectivity: By adjusting pressure and temperature, SFE allows for selective
extraction of specific compounds, minimizing impurities or unwanted extractions.
2. Environmentally Friendly: Supercritical CO₂ is a non-toxic, non-flammable, and
environmentally benign solvent, making the process "green" and sustainable.
3. No Residual Solvent: Since CO₂ can be easily removed by depressurization, there
is no residual solvent left in the extract, which is critical for food, pharmaceutical,
and cosmetic applications.
4. High Efficiency: SFE is highly efficient and can extract a wide range of compounds,
from volatile oils to large, non-volatile substances.
5. Mild Conditions: SFE operates at relatively mild temperatures (often near room
temperature), which helps preserve sensitive compounds such as vitamins,
antioxidants, or essential oils, which might degrade under higher temperatures.
Disadvantages of Supercritical Fluid Extraction:
1. High Initial Costs: The equipment required for SFE is more expensive compared to
traditional extraction methods.
2. Limited Solvent Options: Supercritical CO₂ is the most commonly used fluid, but it
is not suitable for all types of compounds, particularly those that are highly polar. In
such cases, co-solvents like ethanol or methanol may be required, complicating the
process.
3. Complexity: The process requires precise control of temperature and pressure,
which can add complexity to the setup and operation.

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Microwave-Assisted Extraction (MAE)
Microwave-Assisted Extraction (MAE) is an extraction technique that uses microwave
energy to heat solvents in contact with a sample, thereby facilitating the extraction of target
compounds from the sample matrix. This method offers a rapid, efficient, and often
environmentally friendly alternative to traditional extraction techniques like Soxhlet
extraction or maceration, especially for solid-liquid extractions.
Principle of Microwave-Assisted Extraction:
The core principle of MAE is based on the ability of microwaves to generate heat through
the interaction of microwave radiation with polar molecules (like water) and ions in the
solvent and sample matrix. Microwaves cause polar molecules to rotate and ions to
oscillate, producing heat due to friction. This localized heating breaks down the cell walls
of plant tissues or sample matrices, facilitating the release of the desired compounds into
the solvent more quickly and efficiently than conventional heating methods.

Solid-phase extraction (SPE)

Solid-phase extraction (SPE) is a solid-liquid extractive technique, by which compounds
that are dissolved or suspended in a liquid mixture are separated, isolated or purified, from
other compounds in this mixture, according to their physical and chemical properties.
SPE uses the affinity of solutes, dissolved or suspended in a liquid (known as the mobile
phase), to a solid packing inside a small column, through which the sample is passed
(known as the stationary phase), to separate a mixture into desired and undesired
components. The result is that either the desired analytes of interest or undesired
impurities in the sample are retained on the stationary phase. The portion that passes
through the stationary phase is collected or discarded, depending on whether it contains
the desired analytes or undesired impurities. If the portion retained on the stationary phase
includes the desired analytes, they can then be removed from the stationary phase for
collection in an additional step, in which the stationary phase is rinsed with an
appropriate eluent.
It is possible to have an incomplete recovery of the analytes by SPE caused by incomplete
extraction or elution. In the case of an incomplete extraction, the analytes do not have
enough affinity for the stationary phase and part of them will remain in the permeate. In an
incomplete elution, part of the analytes remain in the sorbent because the eluent used
does not have a strong enough affinity.

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Criteria For Selecting Organic Solvent For Solvent Extraction
i. The distribution coefficient of the solute which will be extracted should be high and he
distribution coefficient of the unextractable substance should be low in the selective
solvent.
ii. The organic solvent should be immiscible with the aqueous phase.
iii. It should have good stability. This will amount to the fact that the organic phase should be
capable of withstanding any recycling operations in a solvent extraction circuit without
degeneration.
iv. A difference in densities of the contacting phases is essential and should be as great as
possible. Otherwise emulsification may occur.
v. Solvent should have Iow viscosity . Hence, Iow viscosity is a desirable property. Dissolution
of the Extractant in Iow viscosity diluents modifies this property to a favorable degree.
vi. The interfacial tension should be high for rapid coalescence.
vii. The solvent should cause no corrosion difficulties with common materials of construction
to reduce the cost of equipment.
viii. The solvent should have low toxicity, high boiling and flash points. These mainly avoid
environmental pollution and fire hazards.
ix. It should high metal loading capacity.
x. It should be easily stripped of the loaded metal.

Factors Influencing Extraction

a) pH
b) Molarity of the Acid
c) Metal Ion Concentration
d) Presence of Salting out Agents
e) Presence of Masking (Sequestering) Agent
f) Concentration of the Extractant
g) Nature of Diluents

a) pH
In solvent extraction the equilibrium pH i.e., the pH attained after the two phases have been
contacted to equilibrium is an important factor which affect on separation of extracting species.
The pH will be of great significance in extraction systems listed in the classification scheme under
"Extraction by compound formation".
• The extraction by chelating agents,
• Ex
• Extraction by carboxylic and sulphonic acids and acidic organophosphorus compounds .
All the above process are susceptible to pH variation. The effect of pH on extraction can been seen
from the following diagram.

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Each metal ion exhibits a characteristic extraction curve, with the extraction efficiency increasing
sharply at a specific pH range.

The extraction of each metal ion depends on the pH, with some metal ions being extracted at low
pH values and others requiring higher pH.

Metal-Specific Extraction Ranges:

• Hg(II) is extracted efficiently at very low pH (around 1-2), meaning that Hg(II) forms a stable
dithizonate complex under acidic conditions.

• Ag and Cu(II) are extracted efficiently at slightly higher pH values (around 2-3).

• Pb and Zn require a moderately basic pH (around 5-7) for optimal extraction.

• Cd is extracted efficiently only at higher pH levels, starting from pH 9, indicating that its
dithizonate complex is stable under more basic conditions.

Molarity of the Acid

• The study of the effect of Molarity of the acid on extraction is carried out on the extraction of
metals by salvation or ion — pair formation.

• These investigations are mainly related to the mineral acids and that too mostly to HCl and HN03.

Effect of Metal Ion Concentration

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 • The effect of the metal ion concentration on the distribution ratio of the metal is negligible.
• This Will mean that both tracer and macro amounts of metals may be expected to extracted
to the same extent under similar equilibrium conditions provided the solubility of the
extracting species in the organic phase is not exceeded.
• The relationship between and M(aq) M(org) With the increasing metal ion concentration is
used to find the loading capacity of the extractant.
• These plots known as loading curves or extraction isotherms for the extraction Of Ti (IV), V
(IV), Fe (III), Cu (II) and Zn (II) in toluene solution of Cyanex 923 are shown in Fig below

• In all these plots, the linear part of the curve that the extracting species does not change
• with the increasing metal ion concentrations, thereafter, at a certain point, the loading
condition sets in and no further increase in the metal content of the organic phase is
observed.
• From this, the amount of the metal ion that can be loaded on a particular amount of the
extractant can be calculated and the results expressed in terms of molar ratio.
• Sometimes from this, you can infer the Stoichiometry of the extracted species.

Presence of Salting out Agents

• When inorganic salts are added more and more amount of solute transfer to organic phase
this is called as salting and inorganic substances are called as Salting out Agents
• he salting out effect is explained on the activity of the distributing species and strong ability
of these ions to bind water ( hydration) thereby depleting aqueous phase of the water
molecules to compete.

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 • The magnitude of enhancement in extraction by the added salt depends upon the charge
and ionic size of the cation for a given anion.
• Aluminium and ferric salts are stronger salting out agents than ammonium salts but
analytically, the ammonium salts are more convenient because it is easier to remove them
in the aqueous phase by repeated evaporation with HN03 and HCl. Generally, large
amounts of these salts are added.

Presence of Masking (Sequestering) Agents

• The substances which can form complex with a particular metal ion to prevent from taking
in their usual reactions are called Masking agents
• They are mainly used to prevent particular metals from taking part in their usual reactions
and therefore. the interference of the undesirable elements is removed without the actual
separation step.
• The masked metal forms a water soluble complex most often negatively charged.
• In solvent extraction, the masking agents are used to prevent certain ions from forming
extractable complexes and thus. they increase the selectivity.
• The use of masking agents like cyanide, tartarate, citrate, fluoride and EDTA is restricted to
Chelate systems. In highly acidic solutions encountered in many extraction systems. most
of the masking agents do not function effectively.

Concentration of the Extractant

• Extraction increases with the increasing Extractant concentration.

• Invariably, a straight line is obtained in the plots of log [Extractant] vs log D.
• The slope of the straight line corresponds to the number of Extractant molecules involved in
the formation of the extracting species.

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 Extraction of Metal ions
What Factors do assist in the extraction of metal ions form aqueous
solution to organic solvent?
The basic requirement for a solute (metal ion) to be extractable from an aqueous solution is that it
should be unchanged or can form part of an unchanged ionic aggregate. But if the solute is strongly
ionic or strongly covalent compound then some difficulties are occurred in the solvent extraction
method.

We know, hydrated inorganic salts are highly soluble in water. This value of solubility is actually very
small in organic salts. But organic substances are highly soluble in organic solvents, and less
soluble in water. The extraction of charged species or ionic compounds from an aqueous solution is
not possible unless the charge can be neutralized by chelation or by association with other ionic
species of opposite charge to form a complex that is electrically neutral.

For example, 4-hydroxyquinoline is insoluble in aqueous solution with different metal ions but it
forms soluble chelated compounds in organic solvent (CHCl₃, CCl₄). In this way, metal ion can be
separated by different organic solvents by the formation of chelated complexes.

Thus, The extraction of metal ions from aqueous solution by organic solvent is carried out by
neutralizing the charge and hence by producing neutral species. This can be done in two main
ways-

(a) Formation of chelated complex using suitable organic ligand.

(b) Formation of ion-associated complex

By these two methods, the hydrophobicity of ions can be increased (solubility in organic solvent
can be increased). In each case, the objective is to change the small hydrated metal ion into
species which is more soluble in the organic phase.

(Write Factors affecting chelate formation here)

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 Extraction of Metal ions
Can be done in two ways

1. By ion-pair formation
2. By Chelation

Ion Pair Formation

Solvent Extraction of Fe
1. Formation of FeCl₄⁻ Ion

In aqueous solution, FeCl₃ can react with excess chloride ions (Cl⁻) to form the
tetrachloroferrate(III) ion (FeCl₄⁻):

This reaction occurs especially in the presence of concentrated hydrochloric acid (HCl), which
provides a high concentration of Cl⁻ ions.

2. Protonation of Diethyl Ether

Diethyl ether ((C₂H₅)₂O) is a neutral molecule that can become protonated in a highly acidic
environment:

In concentrated HCl, the abundance of hydrogen ions (H⁺) leads to the protonation of diethyl ether,
forming the diethyl oxonium ion ((C₂H₅)₂OH⁺). This cation is hydrophobic and tends to partition
into the organic phase.

3. Formation of Neutral Ion Pair

The negatively charged FeCl₄⁻ ion associates with the positively charged (C₂H₅)₂OH⁺ ion to form a
neutral ion pair:

FeCl3 + (CH3CH2)2OH+ [FeCl4(CH3CH2)2OH]

This neutral complex is more soluble in organic solvents like diethyl ether than in water due to its
hydrophobic nature.

4. Extraction into Organic Solvent

The neutral ion pair [(C₂H₅)₂OH][FeCl₄] dissolves in the diethyl ether layer. When the aqueous and
organic phases are mixed and then allowed to separate, the iron-containing ion pair moves into the
organic phase, effectively extracting FeCl₃ from the aqueous solution.

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Solvent Extraction of permanganate ion (MnO₄⁻)
MnO₄⁻ is a highly soluble ion in aqueous media, but not very soluble in organic solvents like
dichloromethane (CH₂Cl₂). To extract MnO₄⁻ into the organic phase, it is paired with a large,
hydrophobic cation such as tetraphenylarsonium (Ph₄As⁺). The pairing of Ph₄As⁺ with MnO₄⁻
forms a neutral ion pair, Ph₄As⁺MnO₄⁻, which can dissolve in nonpolar organic solvents.

MnO₄⁻ + Ph₄As⁺ Ph₄As⁺MnO₄⁻

Ph₄As⁺ is a large organic cation, consisting of four phenyl groups attached to an arsenic atom. Due
to its large size and lipophilic nature, it prefers to be in a nonpolar organic solvent rather than in an
aqueous solution. When mixed with an aqueous solution containing MnO₄⁻, Ph₄As⁺ binds to the
MnO₄⁻ ion, forming the neutral ion pair Ph₄As⁺MnO₄⁻. This neutral species can be extracted into an
organic solvent like CH₂Cl₂, where it is more soluble.

Solvent extraction of uranyl ion

The uranyl ion readily forms complexes with nitrate ions (NO₃⁻) in aqueous solution:

This neutral complex, UO₂(NO₃)₂, is more amenable to extraction into organic solvents. The
complex can form multiple nitrates depending on the reaction conditions.

In solvent extraction, the aqueous solution containing uranyl nitrate is contacted with an organic
solvent, typically containing an extractant such as tri-n-butyl phosphate (TBP). TBP forms an
adduct with the uranyl nitrate complex, which is soluble in the organic phase:

Once uranium is extracted into the organic phase, it can be back-extracted (stripped) by
contacting the organic phase with a fresh aqueous solution, often with a lower nitrate
concentration or a different acid (like sulfuric acid). This step separates the uranium from the
organic phase, allowing it to be recovered in a new aqueous phase.

Separation of Metal Ions as Chelate

What is Chelation?
Chelation refers to the formation of a stable complex between a metal ion and a chelating agent
(ligand) that has multiple binding sites. This process is more stable than simple coordination or ion
pairing for several reasons:

1. Multiple Binding Sites: Chelating agents bind to metal ions at multiple points, creating
stronger, more stable complexes.

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 2. Ring Formation: The cyclic structures formed during chelation enhance stability.

3. Thermodynamic Favorability: The process releases water molecules and increases

entropy, making it energetically favorable.

4. Prevention of Hydrolysis: Chelates shield metal ions from hydrolysis, preventing

precipitation.

Here, (II) is more stable because a ring is formed. And a ring formation is much favorable.

The stability of a chelate complex is often quantified by the formation constant (Kf), also
known as the stability constant. It measures how tightly a metal ion binds to a ligand in a
complex. A higher Kf value indicates a more stable complex because the metal ion is more
strongly bound to the ligand.

The general equation for the formation constant is:

[𝑀𝐿]
𝐾𝑓 =
[𝑀][𝐿]

Where
[𝑀𝐿] is the concentration of the metal-ligand complex
[M] is the concentration of the free metal ion, and
[L] is the concentration of the free ligand.

Separation of Metal Ions as Chelate

Such Ligands should be selected which

(i) neutralizes the charge of cation,

(ii) make a stable comple
(iii) Makes the complex soluble in organic solvent

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Principle:

• One of the most common applications of a liquid—liquid extraction is the selective

extraction of metal ions using a chelating agent.
• During the process of Chelation, chelating agent undergoes ionization, the ionisable proton
is displaced by the metal ion when the chelate is formed, and the charge on the organic
compound neutralizes the charge on the metal ion.
• Due formation of chelates size of the complex increases, this complex becomes
hydrophobic in nature because of this more and more solute transferred in organic solvent.
• As most of the chelating agents are less ionize in water for these reasons the chelating
agent is added to the organic solvent instead of the aqueous phase.

Factors affecting chelate formation

a) Basic strength of chelating group: The stability of chelate complex formed with the given
metal ion generally increases with basic strength of the donating agent as measured by the
pKa values. pKa values decides the stability of the chelate complex. Ligands with higher pKa
values (i.e., stronger bases) tend to form more stable complexes with metal ions.

b) Electronegativity of donor group: Electronegativity of basic group (donor group) in the

reagent is also important. Atoms with lower electronegativity tend to donate electrons
more effectively, forming stronger bonds with transition metals.
Example: Sulfur (less electronegative) as a donor atom in dithiozone forms a stronger
chelate than oxygen (more electronegative) in diphenylcarbazone, as sulfur donates
electrons more readily.

c) Ring size: Size of chelate complex is also important. 5 or 6

membered ring chelates are more stable as they have minimum
steric hindrance and no strains. The functional group of ligand must
be situated such that they permit the formation of stable ring. The
chelate stability increases with no. of rings.

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 d) Nature of central metal ion: The charge-to-size ratio (charge density) of the metal ion
affects chelate stability. A higher charge density (i.e., high charge and small size) leads to
stronger interactions between the metal ion and the ligand, thus forming more stable
chelates.
Example: Smaller metal ions with higher charges, such as Fe³⁺ or Al³⁺, tend to form more
stable chelates compared to larger or less charged metal ions like Ca²⁺.

e) Resonance effect: The stability of chelate structure is enhanced by the contribution of

resonance structures of the chelate rings. Resonance within the chelate structure
enhances stability by delocalizing the electron density over multiple bonds, making the
complex more stable.
Example: The copper acetylacetonate complex is more stable than the copper chelate of
salicyldoxime due to resonance stabilization in the acetylacetonate complex.

f) Steric effect: Chelate complexes having bulkier groups experience greater steric strain and
hence are less stable. So, these complexes lead to less efficient extraction.

Extraction by Ion Association Complexes

Extraction by Ion Association Complexes refers to a method in which the species of analytical
interest (typically an ion) associates with oppositely charged ions to form a neutral, extractable
species. This process is an alternative to neutral metal chelate formation, often used in solvent
extraction techniques.

In ion association complex extraction, the analyte forms a neutral complex by combining with an
oppositely charged ion or group of ions. These complexes are more soluble in organic solvents and
can be extracted from aqueous solutions into organic phases. The ability of these complexes to
dissolve in organic solvents depends on the nature of the solvent and the size and stability of the
ion pair or complex.

Mechanism:

1. Ion Pair Formation: The analyte, typically an ionic species, pairs with an oppositely charged
ion (either naturally present or added deliberately) to form a neutral or partially neutral
complex. This pairing reduces the overall charge of the analyte, making it more soluble in
organic solvents
2. Formation of Larger Clusters: At higher concentrations, ion pairs can associate to form
larger ion clusters, particularly in organic solvents with a low dielectric constant. These
clusters are more easily extractable than single ion pairs and are favored by the reduced
polarity of the organic phase.
3. Extraction into Organic Solvent: Once the neutral or partially neutral ion pair or complex is
formed, it can partition into an organic solvent. The efficiency of the extraction depends on
the concentration of the species, the nature of the counterion, and the properties of the
solvent.

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Example of Ion Pair Extraction:

A classic example is the extraction of metal ions from aqueous solutions. When extracting a metal
cation (e.g., Fe³⁺), an anionic organic reagent like a β-diketone (e.g., acetylacetone) is used to form
a neutral complex that can be extracted into an organic solvent such as chloroform or toluene.

Explain- Although Cu2+ forms more stable complex with oxime than VO2+
does, but vanadium may still be extracted in presence of Cu2+ by adding
EDTA
Step 1: Chelation of Cu²⁺ by EDTA

• EDTA (Ethylenediaminetetraacetic acid) is a strong chelating agent and has a higher affinity
for Cu²⁺ than for VO₂⁺. When EDTA is added to a solution containing both Cu²⁺ and VO₂⁺, it
preferentially binds to Cu²⁺, forming a very stable Cu²⁺-EDTA complex.

• This Cu²⁺-EDTA complex is highly stable and remains in the aqueous phase, preventing Cu²⁺
from reacting with other extraction agents like oxime or from moving into the organic phase.

Step 2: Weaker Chelation of VO₂⁺ by EDTA

• VO₂⁺, while it can also bind to EDTA, forms a much weaker complex than Cu²⁺. This means
that VO₂⁺ is not as tightly held in the aqueous phase by EDTA.

• The weaker binding of VO₂⁺ to EDTA allows it to remain more reactive and available for
further chemical interactions or extractions.

Step 3: Selective Extraction of VO₂⁺

• In the presence of a selective reagent like oxime, which can form a complex with VO₂⁺, the
VO₂⁺ ions can be extracted into the organic phase. Since Cu²⁺ is already locked into the
Cu²⁺-EDTA complex, it stays in the aqueous phase and does not compete for the oxime
reagent.

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 • The VO₂⁺ oxime complex can be extracted into the organic solvent, allowing you to separate
VO₂⁺ from Cu²⁺ in the process.

Step 4: Influence of pH

• The pH of the solution plays a significant role in the extraction process. EDTA complexes
with Cu²⁺ are very stable across a wide range of pH, whereas VO₂⁺ complexes might
dissociate or be weaker at certain pH values.

• By adjusting the pH, you can optimize the extraction process for VO₂⁺. Typically, extraction
reagents for VO₂⁺ might work better at a higher pH, where EDTA continues to hold Cu²⁺,
while VO₂⁺ is more available for extraction into the organic phase.

What do you mean by separation factor β of the metal chelates?

If a solution contains two or more solutes (say X and Y), It is observed that when X is extracted,
some amount of Y is also extracted. The extent of this separation is expressed in terms of
separation factor, β. This is related to the distribution ratio of X and Y.
𝐶𝑜𝑟𝑔(𝑋)
𝐷𝑋 𝐶𝑎𝑞.(𝑋)
𝛽𝑋/𝑌 = =
𝐷𝑌 𝐶𝑜𝑟𝑔(𝑌)
𝐶𝑎𝑞.(𝑌)
It indicates the relative ease with which two metal ions can be distinguished from each other
through their respective distribution between the aqueous and organic phases.

Interpretation:

• If β > 1, this means that X is more favorably extracted into the organic phase than Y,
indicating a better separation of X from Y

• If β < 1, this means that Y is more favorably extracted, and X remains predominantly in the
aqueous phase.

• If β = 1, it means both metals are extracted equally, and separation is not possible under the
current conditions.

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