SEPARATION METHODS OF ANALYSIS

Separation methods are very important in analytical chemistry. This is because substances must be
free of impurities before quantitative measurement could be made. It is essential to separate
substances before main analysis. There are two major methods in analysis namely classical method
also referred to as wet chemistry method and instrumental method. It is important to note that all
substances are not present in their pure form. Most are present in form of mixtures, therefore useful
components are separated from the mixture, using various methods of separation. Separation
methods are those methods that can be used to separate two different states of matter such as liquid
and solid.

The following are some of the classical methods used in separation; 1.Hand picking 2. Sieving
3.Sedimentation 4. Decantation 5.Filtration 6.Evaporation 7.Sublimation 8.Condensation
9.Distillation 9. Fractional Distillation 10. Precipitation 11. Extraction, etc.
SOLVENT EXTRACTION

Solvent extraction, also known as liquid-liquid extraction, is a separation process based on the
distribution of a solute between two immiscible phases – a solvent and a feed solution. It is the
most commonly known method of separation. Furthermore, solvent extraction is a process in
which compounds are separated based on their relative solubility. This process exploits varying
solubility of components to selectively separate and concentrate desired substances. For example,
the solution of iodine and glucose can be separated when the solution is shaken with carbon
tetrachloride in a separating funnel. The glucose is miscible with carbon tetrachloride while iodine
is immiscible with tetrachloride, therefore only glucose will be dissolved in carbon tetrachloride
and it will remain in aqueous state. Hence, iodine will be separated from the glucose. Note that,
solvent extraction relies on the variation in the solubility of different compounds in the different
solvents. It is used extensively in fields such as metallurgy, pharmaceuticals, and petrochemicals,
solvent extraction plays a pivotal role in achieving high-purity products and recovering valuable
compounds.

Solvent is therefore a liquid that dissolves another material or substance to form a solution without
a chemical change to the material or to the solvent. There are two types of solvent which are polar
and non-polar solvents.

Polar solvents are solvents that dissolve ionic and covalent compounds. They are always high with
dielectric constant and dipole moment. Examples of polar solvents are water and liquid ammonia.

Non-polar solvents are solvents that dissolve non-polar compounds, they do not have any
permanent dipole moment example benzene and ether.

To separate any substance in a mixture, the choice of solvent must be considered, in the sense that
the solvent to be used depends on the physical and chemical properties of all the substances in the
mixtures. The main objective of solvent extraction is to recover valuable soluble components from
raw materials by dissolving it in an appropriate solvents such that the components can be separated
and recovered from the solvent.

BASIC CONCEPTS IN SOLVENT EXTRACTION

The basic concepts in solvent extraction involve fundamental principles and terms essential for
understanding the process. These basic concepts provide a foundation for understanding the
principles of solvent extraction, guiding the design and optimization of processes for efficient
separation and concentration of components.

Here are key concepts:

1. Solute
- The substance or component that needs to be separated or extracted from a solution.

2. Solvent

- The liquid medium in which the solute is dissolved. It is chosen based on its ability to
selectively dissolve the desired components.

3. Feed Solution

- The initial solution containing the solute that needs to be separated or extracted.

4. Equilibrium Distribution

- The balanced distribution of a solute between the solvent and the feed solution at a particular
point in time.

5. Distribution Coefficient (Kd)

- A measure of how a solute is distributed between the solvent and the feed solution at
equilibrium. It is the ratio of concentrations of the solute in the two phases.

6. Partition Coefficient
 - Similar to the distribution coefficient, it quantifies the distribution of a solute between two
immiscible phases. It is often used interchangeably with the distribution coefficient.

7. Selectivity

- The ability of a solvent to preferentially extract one component over others in a mixture.

8. Mass Transfer

- The movement of solute molecules between the solvent and the feed solution, driven by
concentration differences.

9. Single-Stage Extraction

- A basic extraction process involving a single contact between the solvent and the feed solution.

10. Multistage Extraction

- A more complex extraction process involving multiple stages or units, often in counter-current
flow, to enhance overall efficiency.

11. Extraction Efficiency

- The effectiveness of the extraction process in separating and concentrating the desired
components.

12. Mass Balance

- The accounting of mass entering and leaving the extraction system, crucial for process
optimization.

13. Solvent Extraction Unit

-Equipment like mixers, settlers, and centrifugal extractors used to facilitate the contact and
separation of the solvent and feed solution.
14. Counter-Current Flow

- A process where the solvent and feed solution flow in opposite directions, optimizing
extraction efficiency.

15. Temperature and Pressure Effects

- Manipulating temperature and pressure to control solubility and enhance extraction efficiency.

PRINCIPLES OF SOLVENT EXTRACTION

The principles of solvent extraction are based on the distribution of a solute between two
immiscible phases—commonly a solvent and a feed solution. Understanding and applying these
principles are essential for designing and optimizing solvent extraction processes, ensuring
efficient separation and concentration of desired components. 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
Kd = (same temperature and pressure)
[A]aqueous

Where [ ] represents the concentration and Kd is “partition coefficient” and 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
solubility of the solute in the two phases.

Analytically, the total amount of solute present in each case is better described in distribution ‘D’,
[CA] o/ml
Where D = CA = amount of solute, If there is no interaction, D = Kd.
[CA]aq/ml

Efficiency of Extraction.
It depends on the magnitude of D or Kd and on the relative volumes of the liquid phases
 100D
The % of extraction is given by: £ = D + Vaq/Vo

For equal volumes of aqueous and organic 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 [ DVo +Vaq ]n

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.

For example, 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. 25 cm3 of CCl4 once

2. Batch extraction three times

50
1. [Caq]1 = 0.1 [ 85 ×25 +50 ]1

= 0.0023
0.1−0.0023
% efficiency = ×100
0.1

= 97.7%
50
2. [Caq]3 = 0.1 [ 25 ]3
(85 × ) +50
3
= 2.86 x 10-5

0.1−2.86 x 10−5
% efficiency = = ×100
0.1
 = 99.9%

It is therefore clear that extracting several times with small volumes of organic solvent is
more efficient than one extraction with large volume.

Here are other key principles:

1. Differential partitioning of solute between two immiscible liquid phases (i.e. in some
cases, soluble components can be separated from insoluble or less soluble component
by dissolving them in suitable solvent.
2. The solute partitions between the solvent and the feed solution until equilibrium is
reached. At this point, the distribution of the solute is stable, and the concentrations
remain constant over time:
[A] Conc.of Solute in org Molarity of Solute in Organic Solvent
Kd = [X]aq [A] = =
[Solid]aq Molarity of Solid(aq)

In thermodynamics, it is
Aorg
Kd =
Aaq

Note that in solvent extraction, the solution contains the desired component which must be
immiscible with the rest of the mixture and the substance to be extracted may be solid, liquid or
gas. Therefore proper solvent must be selected. The organic solvent to be used must not react with
the substance to be extracted or even water.

The partition coefficient (Kd) or distribution coefficient is a measure of the ratio of solute
concentrations in the solvent and feed solution at equilibrium. A higher Kd indicates a more
efficient extraction. It is the ratio of the concentrations of the solute in the solvent and feed solution
Conc.Of solid in organic layer
at equilibrium = [S](org) + [X](aq) layer

The distribution coefficient (Kd) quantifies the partitioning of a solute between the solvent and
the feed solution at equilibrium. It is defined as the ratio of concentrations of the solute in the two
phases.
3. Solubility and Selectivity

- The solubility of a solute in the solvent is a critical factor. The more soluble the solute in the
solvent, the higher the extraction efficiency.

- Selectivity refers to the ability of the solvent to preferentially extract certain components over
others, contributing to separation.

4. Solvent Selection

- The choice of solvent depends on factors like solute solubility, selectivity, toxicity, cost, and
environmental impact.

- Different solvents may be suitable for specific applications.

5. Multistage Extraction

- Multistage extraction, employing multiple extraction units in series or counter-current flow,

enhances overall efficiency

6. Safety Considerations

- Due to the potential hazards associated with certain solvents, safety protocols for handling,
storage, and disposal must be followed.
- Environmental impact assessments are crucial in selecting solvents.

TYPES OF SOLVENT EXTRACTION

Solvent extraction, also known as liquid-liquid extraction, comes in various types, each tailored
for specific applications. The choice of the solvent extraction type depends on the specific
requirements of the separation process, the properties of the components involved, and the scale
of the operation. Each type has its advantages and limitations, making it crucial to select the most
suitable method for a particular application.

Here are common types of solvent extraction processes:

1. Single-Stage Extraction

- Involves a single contact between the solvent and the feed solution. Suitable for simple
separations but may not provide high extraction efficiency.

2. Multistage Extraction
 - Utilizes multiple stages or units in series or in a counter-current flow to enhance overall
efficiency. This approach is often employed for complex separation processes requiring high
purity.

3. Counter-Current Extraction

- Solvent and feed solution flow in opposite directions, improving the concentration gradient and
overall extraction efficiency. Common in industrial-scale extraction processes.

4. Continuous Extraction:

- Ongoing extraction process with a continuous flow of solvent and feed solution, allowing for
continuous production. Efficient for large-scale operations.

5. Batch Extraction:

- Extraction is performed in batches with a fixed volume of solvent and feed solution. Useful for
laboratory-scale experiments and small-scale productions.

6. Differential Extraction

- Involves two or more solvents with varying selectivity for different components in the feed
solution. Enables the selective extraction of multiple components.

7. Solid-Liquid Extraction

- Solvent is used to extract soluble components from a solid material, such as in the extraction
of flavors or bioactive compounds from plant material.

8. Liquid-Liquid Extraction in Packed Columns

- Extraction is carried out in columns filled with a packing material to increase the contact surface
between the solvent and feed solution. This is common in large-scale industrial processes.
REQUIREMENTS FOR EXTRACTIVE SOLVENT
The selection of solvents in solvent extraction is a critical aspect that influences the efficiency and
success of the separation process. Several factors need consideration when choosing solvents. Here
are key aspects for the selection of solvents:

1. Solute Solubility

- The solvent should have a high affinity for the solute, ensuring efficient extraction.
Understanding the solute’s solubility characteristics helps in choosing an appropriate solvent.

2. Selectivity

- The solvent should exhibit selectivity, favoring the extraction of the desired component over
others. This is crucial for achieving a high-purity product.

3. Density Difference

- A significant density difference between the solvent and the feed solution aids in the separation
of phases after extraction. This is particularly important for ease of recovery and recycling.

4. Low Viscosity

- Low-viscosity solvents facilitate mass transfer and mixing, contributing to efficient extraction
processes. High viscosity can impede the movement of solutes between phases.

5. Chemical Stability

- Solvents should be chemically stable under the extraction conditions to prevent unwanted
reactions with the solute or other components in the system.

6. Low Toxicity

- Considering safety and environmental concerns, solvents with low toxicity are preferable.
Green solvents that are less harmful to human health and the environment are gaining popularity.

7. Non-reactivity with Equipment

 - Solvents should be compatible with the extraction equipment to avoid corrosion or degradation.
Compatibility with materials used in the construction of the equipment is crucial.

8. Ease of Recovery

- The solvent should be easily recoverable from the extracted product, allowing for cost-effective
and sustainable processes.

9. Regulatory Compliance

- Ensure that the chosen solvents comply with relevant regulations and standards. Regulatory
considerations may affect the selection of solvents, particularly in industries with strict
environmental guidelines.

10. Cost Considerations

- Evaluate the cost of the solvent, including procurement, handling, and disposal. Cost-
effectiveness is an essential factor in industrial processes.

11. Environmental Impact

- Opt for solvents with a minimal environmental footprint. Green solvents, which are
biodegradable and have low environmental impact, align with sustainable practices.

12. Polarity and Polarity Matching

- Understanding the polarity of the solute and selecting a solvent with a compatible polarity
enhances extraction efficiency. Polarity matching improves selectivity.

13. Availability

- Ensure that the chosen solvent is readily available in the required quantities. Availability can
impact the feasibility and reliability of the extraction process.

14. Temperature and Pressure Stability

 - Consider the stability of the solvent under the temperature and pressure conditions of the
extraction process. This is essential for maintaining process integrity.

Balancing these factors based on the specific requirements of the extraction process is crucial for
successful solvent selection. It often involves a trade-off between different considerations to find
the optimal solvent for the desired application.

APPLICATIONS OF SOLVENT EXTRACTION

Solvent extraction finds wide-ranging applications across various industries due to its versatility
in separating, purifying, and concentrating components. Here are some notable applications:

1. Metallurgy

- Metal Extraction: Solvent extraction is extensively used in the mining and metallurgical
industries for extracting and purifying metals from ores. Copper, nickel, cobalt, and rare earth
elements are commonly recovered using solvent extraction processes.

2. Chemical Industry

- Product Purification: Solvent extraction is employed for purifying and separating chemical
compounds in the production of high-purity products. It is a crucial step in the manufacturing of
pharmaceuticals, fine chemicals, and specialty chemicals.

3. Petroleum Refining:

- Hydrocarbon Processing: Solvent extraction is utilized in refining processes to remove

impurities and upgrade hydrocarbons, contributing to the production of high-quality fuels and
petrochemical products.

4. Food and Beverage Industry

 - Oil Extraction: Solvent extraction is commonly used to extract oils from seeds and plant
materials in the food Industry. This process is essential for obtaining vegetable oils used in cooking
and food processing.

5. Pharmaceuticals

- Drug Synthesis: Solvent extraction is employed in pharmaceutical manufacturing for the

purification and isolation of specific compounds from complex mixtures. It plays a vital role in
drug synthesis and formulation.

6. Nuclear Industry:

- Uranium Extraction: Solvent extraction is a key step in the nuclear fuel cycle for extracting and
purifying uranium. It is used in both uranium mining and nuclear waste treatment.

7. Environmental Engineering:

- Wastewater Treatment: Solvent extraction contributes to environmental remediation by

removing and recovering contaminants from industrial wastewater and polluted soils.

8. Biotechnology:

- Biomolecule Isolation: Solvent extraction is used in biotechnology for the isolation and
purification of biomolecules such as proteins, enzymes, and bioactive compounds from biological
sources.

9. Electronics Recycling:

- Metal Recovery from E-Waste: Solvent extraction is employed in the recycling of metals from
electronic waste, aiding in the recovery of valuable materials like gold, silver, and rare metals.

10. Mineral Processing:

-Rare Earth Element Extraction: Solvent extraction is utilized to extract and separate rare earth
elements from mineral concentrates, which are essential in the manufacturing of electronics and
renewable energy technologies.
11. Water Treatment

- Ion Exchange: Solvent extraction principles, particularly ion exchange resins, are used in water
treatment for removing ions and impurities from water sources.

12. Research and Development

- Laboratory Techniques: Solvent extraction is a fundamental laboratory technique used in

research and development across various scientific disciplines.

The diverse applications of solvent extraction highlight its importance in optimizing processes,
recovering valuable resources, and meeting specific purity requirements in industries crucial to
modern life.

13. It is widely used in the lab for refining, isolating and purifying varieties of compounds. It is
used in the production of essential oils e.g. perfumes, flavorings from plants and vegetable oils.

14. It is a technique that is used as a means of sample treatment or clean up to separate analyte
from mixture of components, that will interfere with its detection or quantification. It is used to
determine the content of various organic and inorganic species.

ADVANTAGES
Solvent extraction offers several advantages in various industrial processes, making it a preferred
method for separation and purification in specific applications. Here are key advantages:

1. It gives a better separation effect than chemical precipitation and complete extraction
is obtained.
2. It is a cheap method of separation
3. The method does not destroy a compound
4. Small solvent dosage are required for the extraction method
5. The method is highly efficient
6. The extract can be extracted in many times.

7 It has low energy consumption, easy large production capacity and it has faster distillation

8 It gives a higher degree of selectivity than ion exchange extraction.

Disadvantages of solvent extraction

1. The method is time consuming

2. Technical skills are required
3. Selectivity of the solvent
4. Solvent will also dissolve unwanted product and other substances
5. Through evaporation of solvent, some of the components may be evaporated, hence loss
of components.