Liquid-Liquid Extraction

Submeted by :
Aya Ibrahem
Mohamed Ali
Mohamed Abd El-salam
Niarh Sabry
Table of Contents

Introduction ..................................................................................................................... 1

Definition: ........................................................................................................................ 2

Principle of Liquid-Liquid Extraction (LLE)....................................................................... 4

Steps in Liquid-Liquid Extraction: .................................................................................... 5

1. Mixing/Contacting ................................................................................................. 5

2. Phase Separation ................................................................................................. 5

3. Collection .............................................................................................................. 6

Process of liquid-liquid extraction .................................................................................... 6

Equipment ....................................................................................................................... 6

Advantages ..................................................................................................................... 7

Limitations on choice of extracting solvent: ..................................................................... 8

Applications of liquid-liquid extraction:............................................................................. 8

1. Pharmaceutical Industry .......................................................................................... 8

2. Environmental Analysis ............................................................................................ 8

3. Chemical Engineering and Petrochemical Industry ................................................. 9

4. Food and Beverage Industry ................................................................................... 9

6. Forensic Science ..................................................................................................... 9

7. Mining and Metallurgy .............................................................................................. 9

8. Cosmetics Industry ................................................................................................ 10

9. Agricultural Industry ............................................................................................... 10

10. Waste Treatment and Recovery .......................................................................... 10

References .................................................................................................................... 11
Table of figures

Figure 1 :Sketch of a separatory funnel........................................................................... 3

Introduction
A liquid-liquid extraction transfers an organic compound that is dissolved in an aqueous
phase to an organic solvent, or it is used to transfer unreacted reactants, salts, and other
water-soluble impurities to the aqueous phase while leaving the organic compound of
interest in the organic phase. Immiscible liquids are liquids that never form a homogenous
solution, even when thoroughly mixed. Instead, immiscible liquids separate into different
phases, like oil and water.

A liquid-liquid extraction transfers an organic compound that is dissolved in an aqueous

phase to an organic solvent. To perform a liquid-liquid extraction, first, the aqueous
solution containing the solute is added to a separatory funnel. Then, a non-water-soluble
organic solvent is added to the separatory funnel. When the contents of the funnel are
mixed well, the organic compound partitions into the organic phase based on its higher
solubility in the organic phase than the aqueous phase.

Since the two solvents are immiscible, the two liquids form discrete layers, with the dense
liquid on the bottom and the less dense liquid on the top. Once the two phases settle back
into two layers, they are separated by opening the stopcock at the bottom of the
separatory funnel and allowing one layer to flow out. The liquid that had the solute
removed is called the raffinate, while the liquid that gained the solute is called the extract.

The organic compound is partitioned between the two layers based on its solubility in
each phase. Equilibrium is reached when the chemical potential of the solute is the same
in the two phases. The partition coefficient for a solute, K, is the ratio of the concentration
of the sample in the organic layer divided by the concentration in the aqueous phase. The
partition coefficient is a constant dependent on both the solute and the pair of solvents
used in the extraction. The partition coefficient is an expression of preference of the solute
for each of the two solvents. Solutes with a large partition coefficient have a higher
tendency to be extracted into the organic solvent layer. Solutes with small partition
coefficients prefer to transition into the aqueous phase.

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Determining which solvent pair to use for a liquid-liquid extraction is a vital step. Consider
the following when choosing which solvents to use: First, the solute must be more soluble
in the solvent than in water. Therefore, knowing the partition coefficient of the solute in a
potential solvent pair is necessary. Second, the solvent-pair must be immiscible in water
and not form a homogeneous solution when mixed. Third, the solvents must be inert and
not react with the solute. The solvent should also be volatile so that it can be removed
from the solute easily. The water-immiscible organic solvent generally possesses a non-
polar or low polarity.

Definition:
Liquid – liquid extraction, alternatively known as partitioning and solvent extraction, is a
process that involves two liquids immiscible in each other. Generally, one liquid is of
organic nature, whereas the other is aqueous, which is chosen so that separate
compounds are created. Via contacting and mixing of two liquids, the solute is transferred
from one solvent to the other one. Following this isa phase separation, which involves two
liquids becoming separate. The process involves two solutions, one feed contains the
solute, and another is solvent [1]

Liquid–liquid extraction, also inaccurately known as solvent extraction and partitioning, is

a method to separate compounds based on their relative solubilities in two different
immiscible liquids, usually water and an organic solvent. The term solvent extraction can
also be used for partitioning of compounds between liquid and gas, liquid and solids and
gas and solids. However, this text will exclusively treat partitioning between liquid phases.
The separation of compounds is based on transfer of one or more substances, so-called
extraction, from one liquid phase into another liquid phase. Liquid–liquid extraction is a
basic technique in chemical and radiochemical research laboratories. The simplest
method is a manual one using a separatory funnel (Fig. 1.1). This type of process is
commonly performed after a chemical reaction, often but not always including chemical
complexation, as part of the work-up of the reaction mixture. The term partitioning is
commonly used to refer to the underlying chemical and physical processes involved in
liquid–liquid extraction but may be fully synonymous. Solvent extraction is used as one of

pg. 2
the most important separation methods in industry. Examples are nuclear reprocessing,
mineral ore processing, the production of fine organic compounds, the processing of
perfumes, the production of vegetable oils and biodiesel etc.

Figure 1 :Sketch of a separatory funnel.

Here, the upper (light) phase is the organic liquid, while the lower phase is the aqueous
solution containing the mixture of compounds to be separated. If the specific density of
the organic liquid is higher than for water, the organic phase will be at the bottom. After
vigourous shaking and subsequent phase separation, the target compound has been
transferred from the aqueous phase to the organic phase leaving all other compounds
(“contaminants”) behind in the aqueous phase. The target compound can then be
subsequently stripped from the organic phase back into a pure aqueous phase for further
reactions or treatment. Liquid–liquid extraction is also possible in non-aqueous systems:
In a system consisting of a molten metal in contact with molten salts, metals can be
extracted from one phase to the other. One example is the use of mercury as the molten
metal phase.[2]

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Principle of Liquid-Liquid Extraction (LLE)
Liquid-liquid extraction (LLE) operates on the fundamental principle of transferring a
solute from one liquid phase into another immiscible liquid phase. This process leverages
the differing solubilities of the solute in two immiscible solvents—typically an organic
phase and an aqueous phase.

At its core, the principle is governed by the partition coefficient (K), which quantifies the
distribution of a solute between two immiscible liquids. Mathematically, the partition
coefficient is expressed as:

𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑝ℎ𝑎𝑠𝑒

𝐾=
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑖𝑛 𝑎𝑞𝑢𝑒𝑜𝑢𝑠 𝑝ℎ𝑎𝑠𝑒

The efficiency of the extraction process hinges on the value of KK:

• A high KK indicates that the solute preferentially partitions into the organic phase.

• A low KK suggests the solute remains primarily in the aqueous phase.

The choice of solvent pair plays a critical role in optimizing KK. Solvents are selected
based on their immiscibility, density differences, and ability to selectively dissolve the
target solute while minimizing solubility for impurities. Commonly, solvents like diethyl
ether, chloroform, or hexane are used for organic phases, while water or buffered
aqueous solutions serve as the aqueous phase.

pg. 4
Steps in Liquid-Liquid Extraction: 3 major steps required [3]

1. Mixing/Contacting
During this step, the two immiscible liquids are brought into contact to create a
large interfacial area for mass transfer. The solute diffuses from the feed phase,
where it is present at a higher concentration, into the solvent phase, driven by the
concentration gradient. Effective mixing increases the rate of mass transfer but
must avoid emulsion formation.

Mass Transfer Principles:

o The rate of solute transfer is influenced by the diffusion coefficient,

interfacial area, and solubility limits of the solute in each phase.

o The system typically follows Fick’s laws of diffusion during this step.

2. Phase Separation
Once the solute has transferred to the solvent, the two liquid phases are allowed
to separate based on their immiscibility and density differences. This step is often
enhanced by gravitational settling or centrifugation.

Key Principles:

o Density contrast between the phases ensures stratification.

o Surface tension and coalescence dynamics help achieve clear phase

separation.

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 3. Collection
After separation, the two phases are collected. The raffinate is the depleted phase
that remains after solute extraction, while the extract contains the solute in the
solvent. Further processing may involve recovering the solute from the extract,
often by back extraction, distillation, or evaporation.

Process of liquid-liquid extraction

The principal decision in designing any Liquid-Liquid Extraction (LLE) experiment is the
choice of extraction solvent – this is defined by the relative hydrophobicity of the target
analyte. Compounds which are poorly miscible in organic solvents but highly miscible in
water can be extracted into organic compounds either by (1) repetitive extraction with a
separatory funnel or (2) by using a liquid-Liquid extractor. Extraction methods differ
depending upon the density of the solvent being used. Solvents denser than water will
require different glassware (or supplemental glassware) vs. solvents that are less dense
than water. There are presently a number of setups that can do both. Most simply, LLE is
taking two immiscible phases, one of which is aqueous and the other organic. The two
phases are mixed together (often in a separatory funnel), the compounds within the
sample will then distribute themselves between the two different phases. The liquids can
then separate by filtering and the organic phase is often washed.

Equipment
Liquid–liquid extraction is a basic technique in chemical laboratories, where it is
performed using a variety of apparatus, from separatory funnels to countercurrent
distribution equipment called as mixer settlers. 1 While solvent extraction is often done

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on a small scale by synthetic lab chemists using a separatory funnel, Craig apparatus or
membrane-based techniques normally done on the industrial scale using machines that
bring the two liquid phases into contact with each other. Such machines include
centrifugal contactors, Thin Layer Extraction, spray columns, pulsed columns, and mixer-
settlers.

Advantages
solvent extraction is exclusively used in separation and purification of uranium and
plutonium, zirconium and hafnium, separation of cobalt and nickel, separation and
purification of rare earth elements etc., its greatest advantage being its ability to
selectively separate out even very similar metals. Liquid-Liquid extraction can be
substantially accelerated in microfluidic devices, reducing extraction and separation times
from minutes/hours to mere seconds compared to conventional extractors. Liquid–liquid
extraction is possible in non-aqueous systems: In a system consisting of a molten metal
in contact with molten salts, metals can be extracted from one phase to the other. This is
related to a mercury electrode where a metal can be reduced, the metal will often then
dissolve in the mercury to form an amalgam that modifies its electrochemistry greatly. For
example, it is possible for sodium cations to be reduced at a mercury cathode to form
sodium amalgam, while at an inert electrode (such as platinum) the sodium cations are
not reduced. Instead, water is reduced to hydrogen. Liquid–liquid extraction is also widely
used in the production of fine organic compounds, the processing of perfumes, the
production of vegetable oils and biodiesel, and other industries. 2 Limitations: It is among
the most common initial separation techniques, though some difficulties result in
extracting out closely related functional groups. liquid-liquid extraction is a process that
has many limitations such as extended extraction time, consumption of relatively
excessive quantities of toxic organic solvents, and presence of a possible source of error
due to multiple steps

pg. 7
 Limitations on choice of extracting solvent:
1. Immiscible pair of solvents: water and low polarity organic solvents. The extracting
solvent must be immiscible with the solution to be extracted. Where or a water-based
solution is usually one of the pair. The other solvent is an organic solvent.
2. Good solubility of the target compound. The compound(s) to be extracted, which are
present in a solution, should also be soluble in the extracting solvent.
3. Poor solubility of impurities. Major impurities (e.g., from a reaction) should not be
soluble in the extracting solvent.
4. Volatility of the extraction solvent. The extracting solvent should be sufficiently volatile
so that it can be removed easily from the extracted material by distillation.
5. Toxicity and safety properties of the extraction solvent. It is usually desirable if the
solvent is non-toxic and not flammable. *Some solvents are both toxic and flammable
(e.g., benzene).

Applications of liquid-liquid extraction:

1. Pharmaceutical Industry
• Drug Purification: LLE is used to purify drugs and active pharmaceutical
ingredients (APIs) from complex mixtures.
• Separation of Impurities: LLE is employed to remove unwanted impurities from
drug formulations or intermediate products.

2. Environmental Analysis
• Water Quality Monitoring: LLE is applied to separate organic contaminants from
water samples, such as pesticides, herbicides, and heavy metals, which can then
be analyzed.
• Pollution Control: In industrial effluent treatment, LLE is used to extract toxic
organic compounds (e.g., solvents, oils) from water or wastewater.

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3. Chemical Engineering and Petrochemical Industry
• Solvent Recovery: LLE is employed to recover valuable solvents from industrial
processes, ensuring cost-effectiveness and reducing waste.
• Petroleum Refining: In the extraction of specific hydrocarbons from crude oil or
other sources, LLE plays a role in separating components based on solubility
differences.

4. Food and Beverage Industry

• Caffeine Extraction: The decaffeination of coffee and tea involves using LLE to
extract caffeine from the plant material.
• Natural Product Extraction: Nutraceuticals, flavors, and colorants from natural
sources are often extracted using LLE to ensure purity and quality.
5. Biotechnology

• Protein Isolation: LLE can separate proteins from complex mixtures, such as cell
lysates or fermentation broths, to aid in biotechnology applications like vaccine
production or enzyme purification.
• Metabolite Extraction: In metabolic studies, LLE is used to isolate specific
metabolites from biological samples for analysis.

6. Forensic Science
• Toxicology Testing: LLE is frequently applied to separate drugs, poisons, and other
toxic substances from blood, urine, or tissue samples for forensic analysis.
• Blood Alcohol Concentration Testing: LLE is used to extract alcohol or other
substances from biological fluids for testing in forensic investigations.

7. Mining and Metallurgy

• Extraction of Metal Ions: LLE is used to selectively extract valuable metal ions from
ores or wastewater streams. For example, gold and uranium extraction often
involves LLE to separate metal ions from impurities.
• Separation of Rare Earth Elements: LLE is used in the extraction and purification
of rare earth elements from mining operations.

pg. 9
8. Cosmetics Industry
• Extraction of Active Ingredients: In the production of skincare and beauty products,
LLE is used to isolate active ingredients from plant materials, such as antioxidants
or vitamins.
• Fragrance Extraction: LLE is used to extract essential oils and aromatic
compounds used in perfumes and cosmetics.

9. Agricultural Industry
• Pesticide Removal: In the analysis of agricultural products, LLE is employed to
extract and remove pesticides from fruits, vegetables, and grains.
• Fertilizer Analysis: LLE can help extract specific nutrients or elements from
fertilizers for quality control or composition analysis.

10. Waste Treatment and Recovery

• Hazardous Waste Management: LLE can be used to extract hazardous
substances, such as heavy metals or toxic organics, from waste streams for proper
disposal or recovery.
• Oil Spill Remediation: LLE is employed in the extraction of spilled oil from water,
allowing for cleanup and recovery.

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References
1. (PDF) Liquid -Liquid Extraction. Available from:
https://www.researchgate.net/publication/368660929_Liquid_-Liquid_Extraction
2. Bjørnstad, Tor. (2021). Introduction to liquid-liquid extraction - Lecture Compendium
- Nuclear Chemistry, University of Oslo.
3. https://www.researchgate.net/publication/354814096_Introduction_to_liquid-
liquid_extraction_-_Lecture_Compendium_-
_Nuclear_Chemistry_University_of_Oslo
4. https://chem.libretexts.org/Ancillary_Materials/Demos_Techniques_and_Experimen
ts/Gen eral_Lab_Techniques/Liquid-Liquid_Extraction
5. https://en.m.wikipedia.org/wiki/Liquid%E2%80%93liquid_extraction
6. https://www.chem.ualberta.ca/~orglabtutorials/Interactive%20Tutorials/separation/T
heory /theory6_2.htm
7. https://www.economysolutions.in/blog/liquid-liquid-extractors-principles-
design-and-applications/

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