Extraction

Lecture 11Lecture 11

Associate prof . L.V. VronskaAssociate prof . L.V. VronskaAssociate prof . M.M. MykhalkivAssociate prof . M.M. Mykhalkiv

OutlineOutline

1.1. Extraction. Substance distribution between two Extraction. Substance distribution between two liquids.liquids.

2.2. The main quantitative characteristics of The main quantitative characteristics of extraction.extraction.

3.3. Types of extraction systems.Types of extraction systems.

4.4. The main organic reagents which use in The main organic reagents which use in extraction method.extraction method.

5.5. Usage of extraction in the drug analysis.Usage of extraction in the drug analysis.

1. Extraction. Substance distribution 1. Extraction. Substance distribution between two liquids.between two liquids.

ExtractionExtraction – – is is the process by which a solute is transferred from one phase to a new phase..

Liquid-liquid extractionLiquid-liquid extraction, also known as solvent , also known as solvent extraction and partitioning, is a method to separate extraction and partitioning, is a method to separate compounds based on their relative solubilities in compounds based on their relative solubilities in two different immiscible liquids, usually water and two different immiscible liquids, usually water and an organic solvent. an organic solvent.

ААaqaq ААoror

Process of dissolved Process of dissolved substance transferring substance transferring from one phase to from one phase to another phase, which are another phase, which are immiscible or immiscible or restrictedly miscible, is restrictedly miscible, is named named liquid-liquid –liquid-liquid –partition or partition partition or partition between two phase of between two phase of liquids.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:Partition law of Nernst – Shilov: The relationship of dissolved substance The relationship of dissolved substance

concentration in both phases at constant concentration in both phases at constant temperature is constant and does not depend on temperature is constant and does not depend on concentration of the dissolved substance:concentration of the dissolved substance:

D = CD = CAorgAorg C CAaqu Aaqu

D – the distribution ratio remains constant if there D – the distribution ratio remains constant if there are no processes:are no processes: dissociation or associationdissociation or association polymerisation or other transformations of the polymerisation or other transformations of the

dissolved substancedissolved substance

The ratio of substance activity in one The ratio of substance activity in one certain form in organic solvent phase to certain form in organic solvent phase to its activity in a water phase is namedits activity in a water phase is named a a distribution constantdistribution constant

The distribution ratio and constant are The distribution ratio and constant are connected with substance solubilityconnected with substance solubility

Bn

On

)ML(

)ML(TD a

aK

BA

OA

)S(

)S(D

MainMain conceptsconcepts:: ExtractionExtraction is process of transferring substance of a is process of transferring substance of a

water phase in organicwater phase in organic Extraction reagentExtraction reagent is reagent which with investigated is reagent which with investigated

substance forms compound which then is extractedsubstance forms compound which then is extracted ExtragentExtragent is organic solvent which is used for is organic solvent which is used for

extraction extraction Latent solventLatent solvent ExtractExtract - is a substance made by extracting a part of a - is a substance made by extracting a part of a

raw material, often by using a solvent such as ethanol raw material, often by using a solvent such as ethanol or water. Extracts may be sold as tinctures or in or water. Extracts may be sold as tinctures or in powder form powder form

Re-extractionRe-extraction is process of transferring substance of is process of transferring substance of organic phase in water organic phase in water

Re-extragentRe-extragent

Conditions of a choice of solvent Conditions of a choice of solvent which is used as extragentwhich is used as extragent::

1. Should not mix up with water.1. Should not mix up with water.2. Should be selective.2. Should be selective.3. Should have the big capacity in relation to 3. Should have the big capacity in relation to

extractive.extractive.4. The density of extragent should be difference 4. The density of extragent should be difference

from water density.from water density.5. Should have the minimum viscosity.5. Should have the minimum viscosity.6. Should be inexpensive.6. Should be inexpensive.7. Cannot be explosive.7. Cannot be explosive.

Classification extraction Classification extraction processesprocesses::

Periodical extractionPeriodical extraction - is the process in which - is the process in which separatory funnel (which contain substance separatory funnel (which contain substance which extragent) is shakedwhich extragent) is shaked

Continuous extractionContinuous extraction Countercurrent extractionCountercurrent extraction

1: Stirrer bar/anti-bumping granules2: 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 path4: Soxhlet Thimble5: Extraction solid (residue solid)6: Syphon arm inlet7: Syphon arm outlet8: Expansion adapter9: Condenser10: Cooling water in11: Cooling water out

Schematic diagram of a Soxhlet extractor.

Schematic diagram of a Soxhlet extractor.

2. The main quantitative characteristics 2. The main quantitative characteristics of extraction.of extraction.

Factor or extraction efficiencyFactor or extraction efficiency

R = R = νν (A) / (A) / νν (A) (A)oo

where νν (A) – (A) – moles of solute in organic phase

νν (A) (A)o o – – moles of solute initially present in water phase

Extraction efficiencyExtraction efficiency for for single extraction

)V

Vr(

B

Or

1D

DR

Extraction efficiencyExtraction efficiency::

for multiple (for multiple (mm) extraction) extraction

Separation coefficient (factor)Separation coefficient (factor) ofof A, B A, B ions ions equal relationship the distribution ratio this ionsequal relationship the distribution ratio this ions

mm)1rD(

11R

B

A

D

D

Enrichment factorEnrichment factor ((S)S)

)A(n

)B(n·S

)A(n

)B(nA/B

o

o

A

B)A(B R

RS

Extraction constantExtraction constant for process: for process:

MMn+n++n(HL)+n(HL)OO=(ML=(MLnn))oo+nH+nH++

n)HL()M(

n

H)ML(T

ex

on

on

a·a

a·aK

Extraction constant is function from:Extraction constant is function from:

formation constant of complex, which is formation constant of complex, which is extracted (extracted ())

Acid dissociation constant of extraction Acid dissociation constant of extraction reagent if it forms extraction compound (reagent if it forms extraction compound ())

Distribution ratios of extraction reagent (Distribution ratios of extraction reagent ()) Distribution ratios of extraction complex (Distribution ratios of extraction complex ()) рН of medium (optimum)рН of medium (optimum)

3. Types of extraction systems3. Types of extraction systems

1. 1. HalogenidesHalogenides with covalent linkage: HgCl with covalent linkage: HgCl22, HgJ, HgJ22, ,

SbJSbJ33, AsBr, AsBr33, GeCl, GeCl44, element iodine etc., element iodine etc.

2. 2. Intracomplex saltsIntracomplex salts: dithizonate, dithiocarbamates, : dithizonate, dithiocarbamates, oxyquinolines, oxyns, β-diketonate, and also di-(2-oxyquinolines, oxyns, β-diketonate, and also di-(2-ethylhexyl)-phosphates actinoids, rare-earth and ethylhexyl)-phosphates actinoids, rare-earth and some other elements, etc.some other elements, etc.

3. 3. Complex metal acidsComplex metal acids: HFeCl: HFeCl44, HІnBr, HІnBr44, HSbCl, HSbCl66, ,

etc. etc.

4. 4. coordinatively not solvated (a) and coordinatively coordinatively not solvated (a) and coordinatively solvated (b) saltssolvated (b) salts::

a) Salts tetraphenyl arsonium, tetraphenyl phosphonium etc. a) Salts tetraphenyl arsonium, tetraphenyl phosphonium etc.

b) The compounds which is formed at extraction uranyl b) The compounds which is formed at extraction uranyl nitrate and nitrate of thorium by tributyl phosphate from nitrate and nitrate of thorium by tributyl phosphate from nitrate solutions. nitrate solutions.

5. 5. heteropoly compoundsheteropoly compounds of phosphorus, arsenic, silicon, of phosphorus, arsenic, silicon, vanadium, molybdenum, tungsten etc. vanadium, molybdenum, tungsten etc.

!!!! Most widely is used in extraction process intracomplex !!!! Most widely is used in extraction process intracomplex salts, complex metalo halogenide acids and coordinatively salts, complex metalo halogenide acids and coordinatively solvated (b) saltssolvated (b) salts

4. The main organic reagents which 4. The main organic reagents which use in extraction method.use in extraction method.

8-8-oxyquinolineoxyquinoline reacts with more than 50 elementsreacts with more than 50 elements AcetylacetonateAcetylacetonate forms compound with more than 60 forms compound with more than 60

elementselements Thionyl trifluoride acetoneThionyl trifluoride acetone is used for excretion and is used for excretion and

separation actinoids.separation actinoids. dithizondithizon is used for determination of Pd, Au, Hg, is used for determination of Pd, Au, Hg,

Ag, Cu, Bi, Pt, In, Zn, Cd, Co, etc. Ag, Cu, Bi, Pt, In, Zn, Cd, Co, etc.

!!! !!! It is of great importance in the toxicological analysis.It is of great importance in the toxicological analysis. Sodium Sodium diethyl dithiocarbamatediethyl dithiocarbamate reacts with several reacts with several

tens of elementstens of elements

!!! !!! It is of great importance in the toxicological analysis.It is of great importance in the toxicological analysis.

For increase of selectivity extraction:For increase of selectivity extraction:

Create optimum рН mediumCreate optimum рН medium

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

5. Usage of extraction in the drug 5. Usage of extraction in the drug analysisanalysis

Extraction is used for:Extraction is used for:

1.1. Separation of elementsSeparation of elements

2.2. Concentrating impuritiesConcentrating impurities

3.3. Clearings of the basic component from impurities Clearings of the basic component from impurities in the process of synthesis of substances of drugsin the process of synthesis of substances of drugs

4.4. Definition of the basic component from impurities Definition of the basic component from impurities in the process of synthesis of substances of drugsin the process of synthesis of substances of drugs

5.5. For identification and quantitative definition of For identification and quantitative definition of chemical agent or substances-markers in the chemical agent or substances-markers in the process of the analysis of phytogenesis drugs process of the analysis of phytogenesis drugs

6.6. Increase of sensitivity and selectivity of reactionsIncrease of sensitivity and selectivity of reactions

7.7. Studying of formation constant of complexs Studying of formation constant of complexs

8.8. Studying of substance condition in a solution (a Studying of substance condition in a solution (a charge, polymerisation degree)charge, polymerisation degree)

Reception of extracts, tinctures, fermental Reception of extracts, tinctures, fermental preparations, antibiotics, preparations from a preparations, antibiotics, preparations from a different biological materialdifferent biological material..

Usage of extraction as method of Usage of extraction as method of concentrating and definitionconcentrating and definition

Absolute concentratingAbsolute concentrating is reached at usage of smaller volume of is reached at usage of smaller volume of an organic phase in relation to initial volume of a water an organic phase in relation to initial volume of a water solution.solution.

Relative concentratingRelative concentrating is an increase in impurity concentration is an increase in impurity concentration in relation to the main component.in relation to the main component.

Especially important role extraction is by connection with Especially important role extraction is by connection with physical and physical-chemical methods of the analysis - physical and physical-chemical methods of the analysis - hybrid methods of the analysishybrid methods of the analysis which have such which have such advantagesadvantages: :

High sensitivityHigh sensitivity SelectivitySelectivity SpecificitySpecificity rapid analysis methodrapid analysis method

Extraction of medicinal herbs Extraction of medicinal herbs includes stages:includes stages:

Drying (sometimes it is not necessary)Drying (sometimes it is not necessary) Crumbling upCrumbling up SiftingSifting Selection of optimum extragentSelection of optimum extragent Choice of an optimum technique extractionChoice of an optimum technique extraction Extraction (moisten, passage extragent through Extraction (moisten, passage extragent through

pores, dissolution of substances in the middle of pores, dissolution of substances in the middle of cell, diffusion of substance molecules through cell, diffusion of substance molecules through cellular covers, mass-carrying extraction cellular covers, mass-carrying extraction substances from a surface of particles in substances from a surface of particles in extragent).extragent).

Analytical techniques of Analytical techniques of receptionreception of an extract for the of an extract for the purpose of medicinal herbs analysis on high quality:purpose of medicinal herbs analysis on high quality:

Extraction to a full attritionExtraction to a full attrition (percolation with 1 g (percolation with 1 g medicinal herbs through burret)medicinal herbs through burret)

Single extractionSingle extraction of raw material shot (by boiling 1 g raw of raw material shot (by boiling 1 g raw materials with extragent)materials with extragent)

Equilibrium extraction (for 4-5 hour balance between (for 4-5 hour balance between internal extrageny in medicinal herbs and the external internal extrageny in medicinal herbs and the external extract, analyzes an extract part)extract, analyzes an extract part)

!!! In !!! In the biochemical and toxicological analysisthe biochemical and toxicological analysis extraction extraction is used for excretion of substances from animal and herb is used for excretion of substances from animal and herb tissues, as fresh and dried up.tissues, as fresh and dried up.

Rotary evaporator

Thanks for your attention!Thanks for your attention!