Lecture 11

Extraction

Associate prof . L.V. Vronska

Associate prof . M.M. Mykhalkiv

Outline
1. Extraction. Substance distribution between two
liquids.
2. The main quantitative characteristics of
extraction.
3. Types of extraction systems.
4. The main organic reagents which use in
extraction method.
5. Usage of extraction in the drug analysis.

1. Extraction. Substance distribution

between two liquids.
Extraction is the process by which a solute is
transferred from one phase to a new phase.
Liquid-liquid extraction, also 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.

aq

or

 Process of dissolved
substance transferring
from one phase to
another phase, which
are
immiscible
or
restrictedly miscible, is
named liquid-liquid
partition or partition
between two phase of
liquids.

Separatory funnel for use in a liquid

liquid extraction.

Two phase system, hydrophobic (top) and hydrophilic (bottom) for

measuring the partition coefficient of compounds.

Solid-phase extraction cartridges: (a) disk

cartridge; (b) column cartridge.

Partition law of Nernst Shilov:

The relationship of dissolved substance
concentration in both phases at constant
temperature is constant and does not depend on
concentration of the dissolved substance:
D = CAorg CAaqu
D the distribution ratio remains constant if
there are no processes:
dissociation or association
polymerisation or other transformations of the
dissolved substance

 The ratio of substance activity in one

certain form in organic solvent phase to
its activity in a water phase is named a
distribution constant
T
KD

a ( MLn )O
a ( MLn )B

The distribution ratio and constant are

connected with substance solubility

(S A ) O
D
(S A ) B

Main concepts:
Extraction is process of transferring substance of a
water phase in organic
Extraction reagent is reagent which with investigated
substance forms compound which then is extracted
Extragent is organic solvent which is used for
extraction
Latent solvent
Extract - is a substance made by extracting a part of a
raw material, often by using a solvent such as ethanol
or water. Extracts may be sold as tinctures or in
powder form
Re-extraction is process of transferring substance of
organic phase in water
Re-extragent

Conditions of a choice of solvent

which is used as extragent:
1. Should not mix up with water.
2. Should be selective.
3. Should have the big capacity in relation to
extractive.
4. The density of extragent should be
difference from water density.
5. Should have the minimum viscosity.
6. Should be inexpensive.
7. Cannot be explosive.

Classification extraction
processes:
Periodical extraction - is the process in which
separatory funnel (which contain substance
which extragent) is shaked
Continuous extraction
Countercurrent extraction

Schematic diagram of a Soxhlet extractor.

1:
Stirrer
bar/anti-bumping
granules
2: Still pot (extraction pot) - still
pot should not be overfilled and
the volume of solvent in the still
pot should be 3 to 4 times the
volume of the soxhlet chamber.
3: Distillation path
4: Soxhlet Thimble
5: Extraction solid (residue solid)
6: Syphon arm inlet
7: Syphon arm outlet
8: Expansion adapter
9: Condenser
10: Cooling water in
11: Cooling water out

Schematic diagram of a Soxhlet extractor.

2. The main quantitative characteristics

of extraction.

Factor or extraction efficiency

R = (A) / (A)o
where (A) moles of solute in organic phase
(A)o moles of solute initially present in
water phase

Extraction efficiency for single extraction

D
R
D 1

VO
(r
)
VB

 Extraction efficiency:
for multiple (m) extraction
Rm 1

1
( D r 1)m

Separation coefficient (factor) of A, B ions

equal relationship the distribution ratio this ions

DA

DB

 Enrichment factor (S)

n( B ) o
n(B)
SB / A
n( A )o
n( A )

RB
S B( A )
RA

 Extraction constant for process:

Mn++n(HL)O=(MLn)o+nH+
T
K ex

a ( MLn )o a n
H

n
a n a ( HL )
(M )
o

Extraction constant is function from:

formation constant of complex, which is
extracted ()
Acid dissociation constant of extraction
reagent if it forms extraction compound ()
Distribution ratios of extraction reagent ()
Distribution ratios of extraction complex ()
of medium (optimum)

3. Types of extraction systems

1. Halogenides with covalent linkage: HgCl2, HgJ2,
SbJ3, AsBr3, GeCl4, element iodine etc.
2. Intracomplex salts: dithizonate, dithiocarbamates,
oxyquinolines, oxyns, -diketonate, and also di-(2ethylhexyl)-phosphates actinoids, rare-earth and
some other elements, etc.
3. Complex metal acids: HFeCl4, HnBr4, HSbCl6,
etc.

4. coordinatively not solvated (a) and coordinatively

solvated (b) salts:
a) Salts tetraphenyl arsonium, tetraphenyl phosphonium etc.
b) The compounds which is formed at extraction uranyl
nitrate and nitrate of thorium by tributyl phosphate from
nitrate solutions.
5. heteropoly compounds of phosphorus, arsenic, silicon,
vanadium, molybdenum, tungsten etc.

!!!! Most widely is used in extraction process intracomplex

salts, complex metalo halogenide acids and coordinatively
solvated (b) salts

4. The main organic reagents which

use in extraction method.

8-oxyquinoline reacts with more than 50 elements

Acetylacetonate forms compound with more than 60
elements
Thionyl trifluoride acetone is used for excretion and
separation actinoids.
dithizon is used for determination of Pd, Au, Hg,
Ag, Cu, Bi, Pt, In, Zn, Cd, Co, etc.
!!! It is of great importance in the toxicological analysis.
Sodium diethyl dithiocarbamate reacts with several
tens of elements
!!! It is of great importance in the toxicological analysis.

For increase of selectivity extraction:

Create optimum medium
Use masking (reactions of complexation,
oxidation-reduction, precipitation)

5. Usage of extraction in the drug

analysis
Extraction is used for:
1. Separation of elements
2. Concentrating impurities
3. Clearings of the basic component from impurities
in the process of synthesis of substances of drugs
4. Definition of the basic component from impurities
in the process of synthesis of substances of drugs

5. For identification and quantitative definition of

chemical agent or substances-markers in the
process of the analysis of phytogenesis drugs
6. Increase of sensitivity and selectivity of reactions
7. Studying of formation constant of complexs
8. Studying of substance condition in a solution (a
charge, polymerisation degree)

Reception of extracts, tinctures, fermental

preparations, antibiotics, preparations from a
different biological material.

Usage of extraction as method of

concentrating and definition
Absolute concentrating is reached at usage of smaller volume
of an organic phase in relation to initial volume of a water
solution.
Relative concentrating is an increase in impurity
concentration in relation to the main component.
Especially important role extraction is by connection with
physical and physical-chemical methods of the analysis hybrid methods of the analysis which have such advantages:
High sensitivity
Selectivity
Specificity
rapid analysis method

Extraction of medicinal herbs

includes stages:
Drying (sometimes it is not necessary)
Crumbling up
Sifting
Selection of optimum extragent
Choice of an optimum technique extraction
Extraction (moisten, passage extragent through
pores, dissolution of substances in the middle of
cell, diffusion of substance molecules through
cellular covers, mass-carrying extraction
substances from a surface of particles in
extragent).

Analytical techniques of reception of an extract for the

purpose of medicinal herbs analysis on high quality:

Extraction to a full attrition (percolation with 1 g

medicinal herbs through burret)
Single extraction of raw material shot (by boiling 1 g raw
materials with extragent)
Equilibrium extraction (for 4-5 hour balance between
internal extrageny in medicinal herbs and the external
extract, analyzes an extract part)
!!! In the biochemical and toxicological analysis extraction
is used for excretion of substances from animal and herb
tissues, as fresh and dried up.

Rotary evaporator

Thanks for your attention!