1.

0 INTRODUCTION

In Extraction the mixture of substances is dissociated, by dissolving each component

with one or other solvents which yields two phases – Raffinate Phase (rich in Feed Solvent)

and Extract Phase (rich in Solute) (Sinanoglu, 2004). When the Relative Volatility is 1 the

separation of the components in the mixture is not possible by Distillation and when relative

Volatility is Greater than 1 Extraction method is used for separation of the components. Also,

when the Distillation Method used is too expensive, Extraction process is opted (Halicioglu

and Sinanoglu, 2004).

Solvent extraction methods use non-polar solvents which are miscible with water to

extract the target compound from water by using the greater solubility of the target

compound in the solvent than water. Ideally, one selectively extracts the target compound by

using a solvent whose polarity is close to that of the target compound. Volatile solvents such

as hexane, benzene, ether, ethyl acetate, and dichloromethane are usually used for the

extraction of semi-volatile compounds from water. Hexane is suitable for extraction of non-

polar compounds such as aliphatic hydrocarbons, benzene is suitable for aromatic

compounds, and ether and ethyl acetate are suitable for relatively polar compounds

containing oxygen. Dichloromethane has high extraction efficiency for a wide range of non-

polar to polar compounds (Halicioglu and Sinanoglu, 2004). Dichloromethane is suitable for

simultaneous analysis because of the following advantages: its boiling point is low and easy

to reconcentrate after extraction, it is easy to separate from water because of its higher

specific gravity, and it is non-flammable (Halicioglu and Sinanoglu, 2004).

1
 When extracting compounds which are relatively soluble in water, salting-out

techniques are used in order to increase extraction rates. Adding salt to an aqueous sample

decreases the solvation power of the solution and the solubility of target compounds. This is

useful not only for liquid-liquid extraction but also for headspace and solid phase extraction

methods (Sinanoglu, 2004).

Extraction is commonly achieved by shaking the water sample and solvent in a

separating funnel. However, occasionally large amounts of emulsion are formed, and it is

difficult to separate the solvent from the aqueous phase. If this occurs, the emulsion is often

efficiently dispersed (broken down) by adding either a small amount of ethanol, by

sonicating the mixture in ultrasonic bath, or by adding anhydrous sodium sulfate, or

continuous liquid-liquid extraction can be performed on samples which form emulsions.

Continuous liquid-liquid extraction methods repeatedly circulate solvent in special glassware

but, although this method has good extraction efficiency, it is not suitable for thermally

unstable compounds because the extraction time is long (Sinanoglu, 2004).

A soxhlet extractor is generally a laboratory apparatus (Hardwood et al., 2009) which

was invented in 1999 by Franz Von Soxhlet (Soxhlet, 1999). Extraction of lipid from the

solid material was the main motto behind the designer of the soxhlet extractor. Soxhlet

extraction mainly used when the compounds under consideration has a limited solubility in a

solvent and the impurity is insoluble in that solvent (Hesham et al., 2016).

Soxhlet extraction involves solid-liquid contact for the removal of one or more

compounds from a solid by dissolving it into a refluxing liquid phase. In a conventional

soxhlet device, the solid matrix is placed in a cavity that is gradually filled with the
2
extracting liquid phase by condensation of vapours from a distillation flask. When the liquid

reaches a preset level, a siphon pulls the contents of the cavity back into the distillation flask

thus carrying the extracted analytes into the bulk of liquid (Schantz et al., 1998). Moreover,

the temperature of the system is close to the boiling points of the solvent. This excess energy

in the form of heat helps to increase the extraction kinetics of the system (Hesham et al.,

2016). Besides these soxhlet extraction has its several disadvantages, this method takes many

hours or days to perform; the dilution of the sample in large volumes of solvent etc.

In soxhlet extraction, organic components in solid samples are extracted from the

matrix by continuously washing the solid with a volatile solvent in a specialized piece of

glassware (soxhlet extraction apparatus). This is the most common method for extraction of

organic compounds from solid samples, and is used as an extraction rate standard for the

newly developed extraction method known as supercritical fluid extraction. Non-polar

solvents such as benzene or dichloromethane, polar solvents such as methanol, or mixtures of

polar and non-polar solvents whose boiling points are close to those of ethanol / benzene, or

acetone / hexane are used. Benzene is known to be an especially efficient extraction solvent

for PAHs, and acetone for sulphur-containing compounds. However, soxhlet extraction takes

long time to get high extraction efficiency, and is not suitable for organic compounds which

are thermally unstable (Hesham et al., 2016).

This seminar review is set to vividly discuss solvent and soxhlet extraction

3
2.0 REVIEWS ON SOLVENT AND SOXHLET EXTRACTION

2.1 Solvent extraction

Solvent extraction also known as Liquid-Liquid Extraction refers to an operation in

which the components of the liquid mixture are separated by contacting it with a suitable

insoluble liquid solvent which preferentially dissolves one or more components (Jandera,

2011). In this type of operation, the separation of the components of solution depends upon

the unequal distribution of the components between two immiscible liquids. In liquid

extraction the feed solution is one phase and the solvent used for extraction is another phase.

In Solvent extraction both the liquids i.e. the feed and solvent forms a homogenous mixture

and are separated by contacting it with one another which separates out one of the two liquids

preferentially (Snyder, 2004).

Fig 1: Block Diagram for Liquid-Liquid Extraction

Solvent extraction (Solvent extraction) is one of the favored separation techniques

because of its simplicity, speed, and wide scope. By utilizing relatively simple equipment and

requiring a few time to perform, extraction procedures offer much to the chemists and

4
engineers. Frequently it appears to be the ideal method of separating trace constituents from

large amounts of other substances (Moldoveanu and David, 2013).

Solution diffusion (with or without chemical reactions) is a commonly accepted

mechanism for solvent extraction. The process is often very selective and the isolation of the

solute of interest can usually be made as complete as desired by several repetitions of the

extraction procedure (Moldoveanu and David, 2002).

Even at extraction without chemical reactions at partition of solute neutral molecules

between two immiscible phases, there is a chemical change of the solute in its solvation

environment. More drastic chemical changes of the solute species take place with the

presence of extractant, when different chemical interactions (reversible or irreversible),

formation of new coordination compound, dissociation or association, and aggregation are

possible. This is facilitated, enhanced solvent extraction (Snyder, 2008).

Kinetics of the solvent extraction is a function of the rates of chemical changes that

occur in the system and the rates of diffusion of the various species that control the chemical

reactions. At least one of the chemical or diffusion steps is slow enough to control the overall

rate of the process. So, analysis of mechanisms and kinetics of the chemical and diffusion

steps of the overall process are needed. In chemical technology, the solvent extraction plays

an important role in the purification of chemical reagents and semiconductor materials. This

method is also widely used in nuclear chemistry and technology for the separation of various

radioisotopes and for the reprocessing of nuclear fuels (Sadek et al., 2005).

5
 Using solvent extraction, important theoretical problems concerning the composition

and stability of soluble as well as insoluble complexes can be solved. This quality is very

useful especially for the case when it is not possible to obtain reliable results by other

methods (Vitha and Carr, 2006).

2.1.1 Solvent extraction by Solvation

A. Solubility of Liquids

Solvent extraction is the distribution of a solute or solutes between two immiscible

liquids or phases. Solvent extraction commonly takes place with aqueous and organic

solutions. Solvent extraction is generally carried out at ambient pressures and temperatures.

Sometimes high pressures are used and liquid state can extend up to critical temperature.

Organic phase usually consists of extractant dissolved in diluents (Collander, 2001).

Normally, the organic phase contains a diluent, an extractant, but in some cases, a modifier,

and a synergistic agent. The modifier is added to improve the physical properties of the

system (e.g., to cause phase disengagement after mixing the two phases); synergistic agent is

used for improvement and enhancement of extractant. The aqueous phase, or feed phase,

consists of solute or mixture of solutes, contamination compounds, and acids dissolved in

water (Abraham et al., 2004).

Liquids have some properties that are important in SX techniques. These are

viscosity, surface tension, vapor pressure, density, polarity (electronegativity, dipole

moment), and polarization ability (Leo et al., 2001). Many liquids used in solvent extraction

are polar. Polarity is determined by electric dipole in molecule, since their atoms have

6
different electronegativities. The value of difference is characterized by dipole moment, δd,

e.g., dipole moment of nitrobenzene, δd = 4.0 D (1 Debye unit = 3.34 * 10 -30 C * m) and

water, δd = 1.83 D.

Liquid compounds that have not permanent dipole moment are called nonpolar. These

are many of hydrocarbons. If this liquid is placed in electric field, the electrons of atoms

respond to the external field by atomic polarization which is called relative permittivity and

determined by dielectric constant. The forces between charges, such as ions, of opposite

signs are inversely proportional to the relative permittivity of the liquid. So the dissociation

of molecules into ions strongly depends on the relative permittivity of the solvent used for

electrolyte (Kaliszan, 1997).

Forces that keep the molecules of liquids together and are responsible for the above-

mentioned properties are called as cohesive forces: dispersion (or London) forces, Van der

Waals forces, dipole forces, and hydrogen bonding. Parameter that is called square root of

the cohesive energy density, δ 2 , connects the molar heat of vaporization, ∆HV , with the

liquid volume, V, and temperature, T:

∆ H V −RT
δ 2=
V

The δ parameter is nominated as solubility parameter of the liquid

B. Mixtures of Solutions

The general behavior of the nature, the phase rule of Gibbs says:

p+ f =n+ 2
7
 Where p the number of phases is, f is the number of degrees of freedom, and n is the

number of components.

A system consisting of two immiscible solvents and one solute distributed between

them has one degree of freedom at constant temperature and pressure. The solubility of each

component at equilibrium or miscibility of the solutions is the main question for two-

component, two-phase system in the extraction practice (Moldoveanu and David, 2012).

 Ideal Mixtures

Two liquids very similar in properties such as water and ethanol or benzene and

toluene are mixed practically completely. It means that energy or heat of self-interactions

between molecules of every liquid is similar to that of interaction between molecules of A

and B liquids. In this case the entropy of mixing is maximal and the mixture of such liquids

is called ideal mixture. Chemical potential of A in the ideal mixture is

μ A =μOA + RT ∈x A

where μOA is the molar chemical potential of pure A and x A is the molar fraction of A

in the mixture. A similar equation holds for the B in the mixture. The ideal mixtures obey

Raoult’s and Henry’s laws.

 Real Mixtures

Real (not very diluted) mixture systems have deviations from Raoult’s and Henry’s

laws. Chemical potentials of such mixtures related to activities (thermodynamical

concentrations) of the substance in the mixture but not their concentrations:

8
 μ A =μOA + RT ∈γ A

where γ A is the activity of the substance A in the mixture.

Activity coefficients may be smaller or larger than unity; therefore, deviations from

the Raoult’s and Henry’s laws may be negative or positive.

Distribution ratio remains constant only if the ratio of activity coefficients is

independent of the total concentration of A (or B) in the mixture. This holds (approximately)

in dilute solutions. At the moderate concentrations, this is particularly important in industrial

solvent extraction, the deviation from the Nernst’s distribution law leads to the considerable

errors in preliminary predictions at new solvent extraction processes development

C. Solute–Solvent Interactions (Extractability)

Distribution of a solute between phases takes place according to its solubility in every

phase. The system comes to mass transfer equilibrium. The distribution coefficient (or

constant at equilibrium), KD, of a solute is approximately equal to the ratio of its solubilities

in the organic and aqueous phases. Thus only such compounds can be usefully extracted as

are only slightly soluble in water but are readily soluble in organic solvents (Jandera, 2011).

 The Solubility Parameters

Solubility parameter of the liquid, (Rohrschneider, 2003) δ, connects cohesive forces

with physicochemical potentials ∆G; ∆H of the solutions. This relation holds for ideal and

regular solutions that show ideal entropy effects in mixing solute and solvent, and no

interactions occur besides the cohesive forces between the solute and solvent molecules.

9
Regular solutions exhibit heat changes when mixed, while for ideal solutions, the heat of

mixing is equal to zero. There is no change of state in association or in orientation.

The works correlating various types of cohesive forces with the Hansen solubility

parameters (Snyder, 2004) are summarized by relation:

δ 2
total =δ 2
dispersion +δ 2
polar +δ 2
hydrogen

Here, interactions between the solute and the solvent are described by contributions

from the various types of cohesive forces. In general, the dispersion (or London) forces

dominate.

 Thermodynamic Relations

If concentration of the solute in one phase is constant, the concentration of the solute

in the other phase is also fixed. The relationship between concentrations of solute in each of

the phases led to Nernst’s formulation of the distribution law (Middleditch, 2009).

Distribution constant, Kd (sometimes designated as partition constant, P):

Solute species :conc : org: phase

Kd=
Solute species :conc : aq : phase

Distribution constant has to be distinguished from the distribution ratio, D. When

solute S is present in various differently complexed forms in the aqueous phase and in the

organic phase, [S]tot refers to the sum of the concentrations of all S species in a given phase.

It is important to distinguish between the distribution constant, Kd, which is valid only for a

single specified species, and the distribution ratio, DS, which may involve sums of species

and thus is not constant:

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 Conc : of all species of S∈org : phase [ S ]tot : org
Ds = =
Conc :of all species of S ∈aq : phase [ s ] aq :org

Often in practice, a distribution ratio is less informative than one of percentage

extraction S, %ES:

100 Ds
%E s=
(1+ D¿¿ s) ¿

Extraction percentage curves are particularly useful for designing separation schemes.

Often these curves are not linear but S shaped.

In many extraction systems, some or all of the solvated water molecules must be

removed to obtain a species extractable by organic solvents. These species must, however, be

uncharged because of the low dielectric constants of the organic solvents that are generally

used in extraction procedures.

Organic reagents having one anionic group (OH-), (SH-), etc. and one uncharged basic

group can easily replace water molecules forming neutral, essentially covalent chelate

compounds.

2.1.2 Solvent Extraction with Chemical Reactions (By Complexation)

Species separated by solvent extraction may be organic as well as inorganic. Organic

compounds are usually easily dissolved in organic solvents (lipophilic and hydrophobic).

Inorganic substances are opposite, particularly metal salts (lipophobic and hydrophilic). So,

for extraction of inorganic substances, they must be changed to lipophilic by reaction with

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organic compound extractants (also extracting agents, reagents). This process is described as

reactive extraction or extraction with complexation (Middleditch, 2009).

A. Thermodynamics of Extraction Systems

Extraction from aqueous into organic solutions can be achieved by solvation and

through different chemical reactions. As a rule, they (chemical reactions) are very

complicated and are usually presented through a number of simplified steps. The subdivision

of an extraction reaction into simple steps is useful for understanding the dependence of

distribution ratio values on components of the extraction system variations. These models

allow to determine some of thermodynamic equilibrium constants.

Solutes may be both inorganic and organic non-electrolytes and electrolytes (e.g.,

metal–organic complexes, metal ions soluble in organic solvents through reactions with

organic components). Reactions are considered in the aqueous phase, in the organic phase, or

at the interface between the phases. The system comes to equilibrium state. Let us illustrate

some sub-processes of the extraction process with an example of titanium(IV) extraction

from the strong acidic (>7 mol/kg HCl) aqueous solution by di(2-ethylhexyl)phosphoric acid

(DEHPA) in benzene (Wang et al., 2008).

B. Solute–Solvent Interactions in Aqueous Phase

 Dissociation

Acids (or salts) dissociate in the aqueous phase with a dissociation constant Ka:

HL = H+ + L- Ka = ¿ ¿

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 Solubility in organic solvents is not a characteristic usually attributed to simple metal

salts. As can be expected from their highly ionic nature, most metal salts are strong

electrolytes: molecules dissociated to ions completely or partly.

The ions in the solution are likely to be solvated by the solvent or hydrated in the

aqueous solutions. As a rule, electrolytes have large solubility in aqueous media. Chemical

potential may be formally considered as made by summation of individual ions.

Ionic activities and activity coefficients have a subscript ± for ions with different

charges. The calculation of ionic activity coefficients of an electrolyte in solution is required

for the estimation of solvent extraction systems. The osmotic coefficient of water activity is

also important, related to ability of solutions to dissolve electrolytes and nonelectrolytes

(Chen et al., 2003).

C. Solute–Solvent Interactions in Organic Phase

In organic solution, if its relative permittivity is ε > 40, electrolytes are more or less

completely dissociate into ions. If ε < 10, dissociation is only slight or particularly does not

take place.

In weak polar or non-polar organic solutions, at ε < 40, ion pairing with the solute is

observed. It closes but should be distinguished from the ionic complex formation. Contrary

to metal ion–anionic ligand complexes that have coordinative bonds, the ion pair cannot be

presented as geometrically oriented association (Dean, 1998).

At relative permittivity of organic solvent less than 10, ionic dissociation can be

completely neglected and solutes behave as if they are nonelectrolytes. As a rule these
13
solutions have negligible electrical conductivity. Interactions between solute and solvent or

solute–solute are taking place through solvation. These are donor– acceptor, hydrogen bond,

dipole–dipole, and other cohesive forces interactions. Dipole–dipole and hydrogen bond

interactions can lead to solute aggregation. Linear (head to head or head to tail), chainlike, or

cyclic aggregates can be formed (Handley, 1999).

One more phenomenon, formation of the second organic phase, often happens in

solvent extraction techniques. When organic solution comes to saturation by solute, a new

phase appears. It may be a liquid or a solid. One of the two organic phases is saturated by

solute phase and the second is solvent-rich dilute solution of the solute. According to phase

rule, there are no degrees of freedom in these compositions (Handley, 1999).

2.1.3 Driving Forces of Solvent Extraction

Solutes have different strength of interactions with different solvents or different

solubilities in different solvents. So, in the system of two immiscible or partly miscible

solvents, different solvents become differently distributed between these two phases. This is

a base of solvent extraction technique (Kokosa et al., 2009).

At the simple solute distribution (without any chemical interactions), the transport of

the solute to and from the phase interface is proportional to the chemical potentials or to the

concentration gradients of the solute in the phases and to the partition coefficient KdSF: the

constant giving the concentration ratio of the solute between both phases at equilibrium.

The process of solute extraction is driven by solute concentration gradient, partition

(distribution) coefficient, and Donnan equilibrium coupling. Driving force coefficients KSFex

14
and Kbex may be determined by membrane based extraction experiments (Vitha and Carr,

2006).

Basic features of extractant-mediated transport are as follows: (1) the effect of

extraction is proportional to the extractant concentration and (2) the extraction shows typical

saturation behavior at low solute concentrations, and is close to be independent of [C S] at

high solute concentrations. A very strong complexing extractant becomes fully loaded with

solute even at low concentrations. This leads to the conclusion that the best extractant is not

necessarily the strongest complexing one. Apart from this thermodynamic reason, there may

also be a kinetic reason: strong complexing agents frequently show a slow rate.

2.1.4 Influence of Kinetics Factors

Extraction kinetics is a function of both the kinetics of the various chemical reactions

occurring in the system and the diffusion rate of the various species that control the

chemistry.

Products of any extraction process are usually in a chemical state different from

initial species. Even at simple partition of neutral molecules between two immiscible phases,

there is a chemical change in solvation environment (Sarafraz-Yazdi and Amiri, 2010). Using

extractants that chemically react with the solute, drastic chemical changes take place. They

can be described by subsequent partitioning, interaction (complexation), and diffusion of the

initial species from the bulk phase to the reaction interface and product (solute-extractant

complexes) from the interface to the bulk phase. At first two processes, the solvated water

molecules can be removed from the solute ion; the carrier molecule can undergo an acid

15
dissociation reaction; a new compound, soluble in the organic phase, may be formed with

chelating group of the extractant; extractant–solute complex can undergo changes in

aggregation; and so on. Usually these interactions are going stepwise through several

adducts, including dissociation, aggregation, etc. Every step has its own rate. At least one of

the chemical steps of the overall reaction mechanisms or diffusion rate steps may be slow

enough, and overall transport kinetics would depend on this slow rate. So, we have to

consider both chemical kinetics and diffusion rate steps to determine rate-controlling step for

the overall process (Kokosa, 2012).

Very few tools have been developed up-to-date to investigate chemical changes

occurring at liquid–liquid interfaces, and our knowledge is still limited and is based on

indirect experimental evidence and speculations.

A. Diffusion Transport Regime

Most extraction systems involve stirring of the phases to minimize the time for

diffusion of dissolved species toward and away from the interface. It follows that transport of

species from the bulk phase to a region very close to interface can be considered

instantaneous and the diffusion in the bulk phase can be neglected. But even the most

vigorously stirred systems possess two thin films at the aqueous–organic interface which are

essentially stagnant. These films, often referred to as diffusion films, Nernst films, and

diffusion layers, vary from 50 to 500 mm thick (Jeannot et al., 2010) and can be crossed only

by diffusion processes. The two film model is used here to describe the diffusional transport.

The thickness of the diffusion films never goes down to zero. The time required for the

diffusional crossing of the films by the solute may be longer or comparable with the time
16
required for chemical reactions. So diffusion across the boundary layers may control the

overall kinetics (Jeannot and Cantwell, 1997).

The basic idea of the chemical kinetics–diffusion method is that the solute presented

in the different phases is considered as different chemical species obeying the laws of

chemical kinetics. The general assumptions of the transport may be formulated as follows:

1. Steady-state conditions of the solute transport through the phase interfaces: all fluxes

are necessarily the same. At thin diffusion films only one dimension can be

considered.

2. The overall mass transfer rate of species can be controlled by any of the chemical

reaction–diffusion resistances.

3. The overall mass transfer resistance at steady state is the sum of individual mass

transfer resistances at diffusional regime through the diffusion film and chemical

reaction resistances at the phase interface.

4. Thermodynamic local equilibrium at the interface.

Experience has shown that the film diffusion is very often predominating rate

controlling factor in the solvent extraction practice. The barriers to transport imposed by the

need for diffusion across diffusion layers can be minimized by decreasing film thickness or

by increasing the mobility of the diffusible species (Jeannot and Cantwell, 1997). The

thickness of the diffusional films depend on stirring rate of the phases and type of the stirrers

used, on the geometry of the extraction equipment, and on the viscosity and density of both

phases. The thickness, up to a certain limiting value, is inversely related to mechanical

energy supplied (e.g., by stirring) (Henschke and Pfennig, 1999). Viscosity and density of the
17
liquids used as well as equipment geometry also affect film thickness but interfacial films

apparently cannot be completely eliminated.

B. Chemical Reaction Kinetics Regime Transport

For the last time more and more investigations report that chemical reaction kinetics

play sometimes critical role for overall extraction process kinetics (Michulec and Wardencki,

2006). When one or more of the chemical reactions are sufficiently slow in comparison with

the rate of diffusion to and away from the interfaces, diffusion can be considered

“instantaneous,” and the solute transport kinetics occur in a kinetic regime. Kinetic studies of

chemical reactions between solute and reagent (extractant) seek to elucidate the mechanisms

of such reactions. Information on the mechanisms that control solvent exchange and complex

formation is reported briefly below.

 Complexation–Decomplexation

Two series of chemical reactions mechanisms and their kinetics have to be analyzed:

1. Solute partition and chemical interactions with extractant (or solvents) and formation

of solute–extractant complex (forward extraction or complexation).

2. Solute release from organic phase with chemical interactions and destruction of the

complex (decomplexation or back extraction) and partition of the solute between

organic and aqueous strip phases.

In the solvent exchange, the composition of the coordination sphere often changes,

either because of the formation of complexes between the solutes and a complexing reagent,

preferentially soluble in an organic phase, or because of the replacement of a ligand in the

18
aqueous phase solute complex with another more lipophilic one in the organic phase. Solvent

exchange and complex formation are special cases of nucleophilic substitution reactions. The

basic classification of nucleophilic substitution is found on the consideration that when a new

complex is formed through the breaking of a coordination bond with the first ligand (or

water) and the formation of a new coordination bond with the organic ligand, the rupture and

formation of the bonds can occur with different rates and through the formation of transition

intermediates (adducts) (Michulec and Wardencki, 2006).

The rate at which solvent molecules are exchanged between the primary solvation

shell of an ion and the bulk solvent is of primary importance in the kinetics of complex

formation from ions in aqueous solutions. In both water exchange and complex formation, a

solvent molecule in the solvated ion is replaced with a new molecule (another water molecule

or a ligand). Therefore, strong correlations exist between the kinetics and the mechanisms of

the two types of reactions. Observations (Ganjali et al., 2010) showed that the rates and

activation parameters for complex formation are similar to those for water exchange, with the

complex formation rate constants usually about a factor of 10 lower than those for water

exchange with little dependence on the identity of the ligand. This means that, at least as a

first approximation, the complex formation mechanism can be described by the rapid

equilibrium formation.

 Liquid–Liquid Interface

Contact, interaction, and transfer of chemical species on the liquid–liquid interface of

two immiscible phases have to be mentioned in the general consideration of chemical

kinetics. Little direct information is available on physicochemical properties (interfacial

19
tension, dielectric constant, viscosity, density, charge distribution, etc.) of the interface. The

physical depth of the interfacial region can be estimated in the distance in which molecular

and ionic forces have their influence. On the aqueous side (monolayers of charged or polar

groups), this is several nanometers; on the organic side is the influence of Van der Waals

forces. These interfacial zone interactions may slower exchange and complex formation

reactions, but as a rule enough fast to be not rate controlling for the most chemical

interactions on the interface (Ganjali et al., 2010).

All considerations, presented for the kinetics of forward extraction reactions, may be

applied in the reverse mode to the chemical interactions at strip interface with the complex

destruction (decomplexation or back extraction), the solute release, and partition between

organic and aqueous strip phases. It has to be taken into consideration two basic differences:

quite different thermodynamic conditions on the organic–strip phase interface that may lead

to different interaction mechanisms and kinetics and different, more slow kinetics of complex

destruction (comparing to the complexation), especially at destruction of aggregates or

oligomers that can be formed in the organic phase at high initial concentration of the solute

(Viswanath et al., 2007).

Spectrometric NMR studies showed that the complexes can be kinetically stable

(Jeannot et al., 2010) and, as a consequence, decomplexation rates can be very slow.

Recently, at cation interaction experiments with different calix crown ether derivatives,

(Henschke and Pfennig, 1999) it was proven that the rate of decomplexation can be rate

controlling in the extraction–back extraction techniques.

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C. Mixed Diffusional–Kinetic Transport Regime

When both chemical reactions and film diffusion processes occur at rates that are

comparable, the Solvent extraction kinetics takes place in a mixed diffusional–kinetic

regime, which, in engineering, is often referred to as “mass transfer with slow chemical

reactions.” This is the most complicated case, since the rate of extraction must be described

in terms of both diffusional processes and chemical reactions, and a complete mathematical

description can be obtained only by simultaneously solving the differential equations of

diffusion and those of chemical kinetics. The unambiguous identification of the extraction

rate regime (diffusional, kinetic, or mixed) is difficult from both the experimental and

theoretical viewpoints (Michulec and Wardencki, 2006). Experimental difficulties exist

because a large set of different experimental information. Very broad range of several

chemical and physical variables is needed. Unless simplifying assumptions can be used,

frequently the differential equations have no analytical solutions, and boundary conditions

have to be determined by specific experiments.

 Identification of the Rate-Controlling Transport Regimes

The experimental identification of the regime that controls the process kinetics is, in

general, a problem that cannot be solved by reference to only one set of measurements. In

some systems, a definite situation cannot be obtained even when the process rate is studied as

a function of both hydrodynamic parameters (viscosity and density of the liquids, geometry

of the module, stirring or flow rates) and concentrations of the chemical species involved. It

is because the rates may sometimes show the same dependence on hydrodynamic and

concentration parameters, even though the processes responsible for the rate are quite
21
different (Snyder, 2004). For a correct hypothesis on the type of regime that controls the

transport kinetics, it is necessary to supplement kinetic investigations with other information

concerning the biphasic system. This may be the interfacial tension, the solubility of the

extractant in the aqueous phase, the composition of the solutes in solution, and so on. The

criteria that are often used to distinguish between a diffusional regime and a chemical kinetic

regime are as follows:

1. Comparison of the heat transfer and the mass transfer coefficients. If the same

dependence of the heat transfer coefficient and the mass transfer coefficient on the

stirring or flowing rate of the phases is observed, the conclusion can be reached that

the transport occurs in a diffusional regime (Michulec and Wardencki, 2006).

2. The reference substance method. This method is based on the addition of another

inert component with known diffusion rate. By following the simultaneous transfer of

the species of interest and of the reference component as function of the

hydrodynamic conditions, a diffusional regime will be indicated by a similar

functional dependence, whereas a kinetic regime is indicated by a sharply different

one. Criteria 1 and 2 are complicated and may be used only occasionally to evaluate

the transport regime.

3. Evaluation of parameter a: relation between diffusion and reaction kinetics regimes.

4. Evaluation of the activation energy of chemical reactions. This criterion is not always

very meaningful, since many chemical reactions occurring in separation processes

exhibit activation energies of only a few kilocalories per mole, i.e. having the same

order of magnitude as those of diffusional processes.

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 5. Dependency of the transport rate on the rate of stirring or flowing of the phases.

2.2 Soxhlet Extraction

2.2.1 Principles of Soxhlet Extraction

Soxhlet extraction is a very useful tool for preparative purposes in which the analyte

is concentrated from the matrix as a whole or separated from particular interfering

substances. Sample preparation of environmental samples has been developed for decades

using a wide variety of techniques (Ballschmeter, 2003). Solvent extraction of solid samples,

which is commonly known as solid-liquid extraction (also referred to as leaching or

Lixiviation in a more correct use of the physicochemical terminology), is one of the oldest

methods for solid sample pretreatment (Fifield and Haines, 2005). Conventional Soxhlet

extraction remains as one of the most relevant techniques in the environmental extraction

field. This assertion is supported by the double use of conventional Soxhlet: (1) as an

extraction step in a given method, and/or (2) as a well-established model for comparison of

new extraction alternatives.

In conventional Soxhlet, the sample is placed in a thimble-holder and during

operation is gradually filled with condensed fresh solvent from a distillation Sask. When the

liquid reaches an overflow level, a siphon aspirates the whole contents of the thimble-holder

and unloads it back into the distillation flask, carrying the extracted analyses in the bulk

liquid. This operation is repeated until complete extraction is achieved. This performance

makes Soxhlet a hybrid continuous discontinuous technique. Inasmuch as the solvent acts

stepwise, the assembly can be considered as a batch system; however, since the solvent is re-

23
circulated through the sample, the system also bears a continuous character (Luque-de-Castro

and Da-Silva, 2007).

Figure 1 shows a scheme of a conventional Soxhlet device. As can be seen, Soxhlet

extraction is a very simple technique. This simplicity makes the procedures for different

samples very similar. For this reason, an overview of its extensive application in the

environmental field during the last two decades is presented here, which cover the kind of

samples, analytes, solvents, etc. used and the role of Soxhlet extraction in the overall

analytical process.

Figure 1: Soxhlet extraction apparatus.

24
2.2.2 Use of Conventional Soxhlet Extraction for Leaching of Organic Pollutants

Organic pollutants present in solid environmental samples from natural or man-made

sources are most of the time properly extracted with organic solvents in a Soxhlet device.

The following sections show how conventional Soxhlet extraction is used as a technique for

separation of the analytes from the solid matrix. The pollutants are classified into three

groups depending on the matrices in which they are present: air, solid and liquid samples. It

is worth noting that, in spite of the solid character of particulates, the samples are classified

as a function of the medium in which they are present (Luque-de-Castro and Garcia-Ayuso,

1998). Thus, airborne and water particulates are classified as air and liquid samples,

respectively.

A. Organic Pollutants in Air

Organic pollutants are in the gas phase of the atmosphere and are associated with

airborne particulate matter. Sampling of organic pollutants is usually carried out by filters

through which a large volume of air is circulated. After filtration, the filter is extracted with

an appropriate solvent and the target analytes are removed in the extract (Poole and Poole,

2006). When the extract is not suitable for direct individual separation/determination a prior

clean-up stage must be applied. These and other aspects are discussed below.

Polycyclic aromatic hydrocarbons: Polycyclic aromatic hydrocarbons (PAHs) and their

derivatives are among the most studied environmental pollutants. This is due to both their

continuous emissions from combustion and their biological activities, such as toxicity,

mutagenicity and carcinogenicity. Determination of PAHs from air requires a suitable

25
sampling device, including an aspiration pump, which retains the air particulates on glass or

quartz fibre, cellulose or paper filters. However, the filter is not the sole collection medium

for PAH-containing small size aerosols. Chemicals such as Tenax GC, PUFs or Amberlite

XAD-2 resins should provide a back up to these filters by retaining PAHs not trapped by the

filter. A layer of activated charcoal between two filters is used for collection of gaseous

components (Fifield and Haines, 2005).

The adsorbed compounds are extracted by Soxhlet into different organic solvents

such as toluene, benzene, cyclohexane, tetrahydrofuran, dichloromethane and liquid CO2.

Clean-up extract procedures are mainly performed by the use of silica gel (SFC, LLE and LC

are also used), and the individual separation/determination stage involves HPLC-UV and

GC-MS. A less common technique for PAH determination is TLC-UV.

Polychlorinated dibenzo-dioxins (PCDDs) and polychlorinated dibenzo-furans

(PCDFs): Analysis of dioxins has become an issue of major importance because of their

carcinogenic nature. The main source of dioxin emission is combustion (in waste incineration

and the steel industry). In comparison with the wide variety of methods used for the

determination of PAHs from air, the method for determination of PCDDs and PCDFs is well

established and only some minor modifications are found in the literature. These compounds

are sampled by splitting the air into two phases. The split involves glass fibre filters, which

retain airborne particulates, and PUF solid sorbents, which retain vapours (Luque-de-Castro

and Da-Silva, 2007). The PUF sorbents are fortified with a range of 13C-labelled PCDDs and

PCDFs before sampling (sometimes spiking precedes the sampling step). The same spiked

procedure is applied to particulate phases before extraction (Ballschmeter, 2003).

26
 The filter and foam are then extracted by Soxhlet with toluene (benzene/ethanol and

dichloromethane have also been used but less frequently than toluene), followed by an acid-

base clean-up step, then drawing of the extract through micro-columns of silica gel, alumina

and carbon (sometimes a chromatographic clean up is applied before). Individual separation

of the analytes and determination are performed by high-resolution GC-EIMS-SIM (Luque-

de-Castro and Garcia-Ayuso, 1998).

Polychlorinated biphenyls (PCBs) and other chlorinated compounds: A wide variety of

pollutants other than PCDDs and PCDFs contain chlorine. This makes them very harmful

due to their activity in the atmosphere. PCBs and other compounds (chlorinated solvents,

halogenated methoxybenzenes (halogenated anisoles), polychlorinated naphthalenes, etc.) are

the most representative chlorinated compounds in addition to OCPs (alpha and gamma

hexachlorocyclohexane (HCHs), chlorothalonil, dichlofiuanid, toxaphene, chlorpyrifos,

alachlor, etc) (Poole and Poole, 2006). Sampling of these compounds is similar to that

described in the previous two sections and either the adsorbent used or the extraction solvent

and postextraction procedures applied are widely documented in the literature. Thus, the

performance of different sorbents, such as Chromosorb 102, Porapak R, Supelpak-2,

Amberlite XAD-2, Amberlite XAD-4, Carbonaceous Ambersorb XE-340 and polyurethane

foam, has been evaluated with use of atmospheres containing known concentrations of OCPs

(Poole et al., 2000).

The most efficient trap for HCH and PCBs was found to be two cartridges containing

PUFs-Tenax-GC sandwich traps, connected in series. Halogenated anisoles and

hexachlorobenzene (HCB) have been sampled from air using a high volume sampling

27
technique in which air was pumped through two layers of solid sorbent: the upper sorbent

layer was a mixture of silica gel 60/ENVI-Carb or ANGI-Sorb 5B/ANGI-Sorb 10B and the

lower sorbent layer was silica gel 60/ENVICarb or ANGI-Sorb 2.5B. These solid sorbents

are Soxhlet extracted with organic solvents, mainly dichloromethane (but also with others

such as petroleum ether, ethyl ether, hexane, acetone and mixtures) and, after the appropriate

clean up, the detection/ determination step is developed mainly by GC-ECD (Prichard et al.,

2006).

Other pollutants usually determined in air: In addition to PAHs and chlorinated pollutants

from the atmosphere, there are some other families of pollutants that have a significant effect

on the environment. Thus, alcohols and phenols, organophosphorous compounds, anilines

and benzidines, aliphatic hydrocarbons, etc., can be included in this classification (Poole and

Poole, 2006). The procedures for determination and the general characteristics of the

chemicals and instruments used (solid sorbents, extractant, extraction time, clean up and

detection/determination) are similar to those discussed in previous sections.

Organic pollutants in solid samples: Organic pollutants are present in a wide range of

environmental solid samples. Thus, soil, sediment, sewage sludge and ash are the most

commonly studied matrices in the environmental field. All these matrices can be reached by

conventional Soxhlet extraction. There are two criteria that solid samples must meet before

extraction: (1) they must be finely divided (in order to improve the sample-solvent contact),

and (2) sample moisture must be carefully controlled. After the extraction step by an organic

solvent, a clean-up procedure is necessary due to the co-extraction of both fat residues and

other interferent substances (Poole et al., 2000).

28
 There are some other pollutants that are frequently determined in solid samples.

These compounds (in general, the same as those covered in Organic Pollutants in Air) are

usually in trace amounts in the environment. Thus, organic pollutants such as aliphatic

hydrocarbons, aldehydes, non-chlorinated phenols, cresols, anilines and benzidines, VOCs

(mainly organic solvents), phthalates, amines, non-chlorinated pesticides, etc., are also

determined due to their importance in the environment. Soxhlet extraction has shown its

suitability as a technique for separation of these pollutants from solid environmental matrices

(Luque-de-Castro and Garcia-Ayuso, 1998).

B. Organic Pollutants in Water

Water is the most important liquid in the environment. A wide range of human

activities, such as mining, coal and fuel combustion, industrial and agricultural processes,

domestic sewage, etc, contribute to the pollution of the aquatic environment (Ballschmeter,

2003). However, the key contribution to water pollution is the solubilization of pollutants.

Thus, the study of pollutants in water can be divided into pollutants that are solubilized in

water (mainly inorganic pollutants) and those present as the solid phases of the aquatic

medium, such as sludge, sediment, particulates and biological species (organic and inorganic

pollutants) (Fifield and Haines, 2005).

The way in which sludge and sediment are Soxhlet extracted in order to isolate the

analytes from the solid matrix has been discussed in previous sections. This section is

therefore devoted to the analysis of organic pollutants (mainly PCBs and pesticides) from

water and associated particulates. In spite of the fact that biological samples are also a part of

29
the environment, they are considered to be a matter concerning biochemistry and toxicology

and, therefore, beyond the scope of this article (Luque-de-Castro and Da-Silva, 2007).

It is obvious that Soxhlet extraction is not a suitable method for direct separation of

analytes from liquid sample, but that it must be used after a previous filtration step. This

procedure is very similar to that followed for air samples. The two phases existing in water

within suspension matter samples (liquid and particulate) are split by filters (paper, glass-

fibre or quartz-fibre) and solid sorbents (PUFs, granular activated carbon, Aquapak 440A,

Separon SE, ODS gel and Amberlite XAD-2, -4 or -7 resins). The solid sorbents and the

particulate matter constitute the solid sample to be subsequently extracted by Soxhlet.

Collection of the solid matter by centrifugation is an alternative to filtration. Some of the

procedures found in the literature are discussed below.

PCBs and OCPs are Soxhlet extracted from solid particulate matter with

dichloromethane. After silica gel or Florisil clean up in the presence of activated Cu, analyses

are developed by GC-ECD (or GC-MS). The determination of organophosphorus and

organonitrogen pesticides in solid particulate matter from surface water is developed by

dichloromethane Soxhlet extraction and GC-NPD. The determination of PAHs from water

samples requires hexane/acetone Soxhlet extraction, cleanup on both an Al2O3-Na2SO3

column and silica column, and finally, individual separation by HPLC and Suorimetric

detection (Poole et al., 2000).

Many aquatic organisms accumulate pollutants inside their tissues by

bioaccumulation. This behaviour is used in pollution surveillance programmes, due to the

following advantages it provides: (1) the analyses of soil, air, water, etc. yield levels of
30
pollutants present at the time the samples were taken, whereas those observed in bio-

accumulator species reflect the level over a period of time; and (2) pollutants concentrate in

biological species at high levels, and can therefore be monitored by analytical techniques

with relatively high detection limits (Prichard et al., 2006).

The most relevant field in which biological samples are used is in the analysis of the

aquatic environment. Fish, mussels and a number of other species are studied in order to

evaluate pollution levels in the surrounding environment. The pollutants studied are the same

as in previous sections, and Soxhlet extraction has great relevance as a pretreatment

technique due to the solid character of the matrix. In spite of this, one of the most relevant

drawbacks in Soxhlet extraction of these samples is their high water content (the presence of

water in samples subjected to Soxhlet extraction constitutes a shortcoming whose importance

is a function of the amount of water). Thus, it is necessary to macerate the sample initially

with anhydrous Na2SO4. After this, a conventional Soxhlet extraction of the mixture with an

organic solvent (depending on the nature of the analytes) is performed (Warner, 2006).

2.2.3 Use of Conventional Soxhlet Extraction for the Leaching of Inorganic Pollutants

The application of conventional Soxhlet extraction in the field of inorganic pollutants

has been developed to a much less extent than that of organic pollutants. There are in the

literature only a few applications of Soxhlet extraction to inorganic compounds. Soxhlet

extraction is used mainly as a clean-up step prior to the determination of inorganic pollutants

with the aim of removing organic substances in the extract. As an exception to this, metals

have been determined in the extract after a Soxhlet step. This is possible either when metals

are forming organometal compounds or are concentrated by sorption on PUFs impregnated

31
with an organic substance. However, the suitability of Soxhlet extraction for the isolation of

inorganic pollutants is poor and some other techniques such as hydrolysis, digestion,

distillation, etc. are recommended for this purpose (Chen and Pawliszyn, 2005).

2.2.4 Improvements in Soxhlet Extraction

Soxhlet extraction has been the most frequently used technique for isolation of

organic pollutants from environmental samples for the last twenty years. However, the use of

new extraction techniques that overcome the drawbacks associated with Soxhlet is, today,

one of the most promising research lines in the field of solid sample treatment (Daimon and

Pawliszyn, 2002).

The most significant drawbacks of Soxhlet extraction are the long time required for

the extraction and the large amount of organic solvent wasted, which is not only expensive to

dispose of but which can cause environmental pollution itself. Moreover, the conventional

device is not easily automated (Eisert and Pawliszyn, 2007). There are two different ways in

which to circumvent the drawbacks of conventional Soxhlet extraction, namely: (1) the use

of one of the new alternatives (such as SFE, MAE, ASE, etc.); and (2) the improvement of

conventional Soxhlet. As this article is devoted to Soxhlet extraction, the following sections

discuss only the latter way that is, improving the shortcomings of the conventional device

while keeping its positive characteristics (Eisert and Levsen, 2003).

A. High-pressure Soxhlet extraction

High pressure in Soxhlet devices is achieved by placing the extractor in a cylindrical

stainless-steel autoclave or by the use of either commercial or laboratory-made supercritical

32
Suid-Soxhlet extractors. Thus, PAHs and PCBs and be removed from environmental samples

using HPS with liquid CO2 in working conditions close to those corresponding to the

supercritical state of the extractant (Fromberg et al., 2006). The main drawback of this

alternative is the change from supercritical to liquid state of the extractant, which affects

Soxhlet performance.

B. Automated Soxhlet (Soxtec HT and Buchi B811)

Commercial automated Soxhlet devices perform the extraction with similar precision

to conventional Soxhlet but with a significant saving of time and extractant. The most

relevant characteristic of a Soxtec system is the possibility of developing three different

steps, namely, boiling, rinsing and recovery of the solvent, by switching a lever. The B811

extractor is able to perform the same steps as a Soxtec device but it can also work as a

conventional Soxhlet. The overall performance of the B811 extractor is computer controlled.

The analysis of organic pollutants from soil and sediments is an example of the methods

developed for use with this device (Daimon and Pawliszyn, 2002).

C. Focused microwave-assisted Soxhlet extraction (Soxwave and FMASE)

The Soxwave is a commercial system with an operational performance similar to that

of Soxtec HT. The system performs the same three steps but with two significant differences:

(1) a different heating source (microwave instead of electricity) is used; and (2) the sample is

also irradiated with microwave energy, making it easier to rupture the analyte-matrix bonds

(Fromberg et al., 2006).

33
 The main drawback of Soxwave is its dependence on the extractant dielectric

constant. Thus, efficient extractions are only obtained with polar solvents (due to the

characteristics of microwave irradiation) and, consequently, this device is not as universal as

a conventional Soxhlet is. Moreover, the energy the analytes receive is at least as high as that

necessary to reach the boiling point of the solvent, which can cause degradation of

thermolabile analytes. Some applications of Soxwave have been developed in the

environmental field and, due to its suitability for water-based extractions, quantitative

extractions have been achieved in the isolation of metals from solid samples such as coal or

soils (Hageman et al., 2008).

FMASE is the last of the improvements carried out on the conventional Soxhlet

extractor. In fact, the FMASE device works as a conventional Soxhlet, but the cartridge zone,

where the extractant and sample are in contact, is placed in the microwave cavity of a

specially designed focused microwave oven. The similar performance with respect to its

conventional counterpart makes FMASE a suitable alternative for almost all the applications

developed in a conventional Soxhlet that can be developed without changes, except in the

time required for quantitative extraction (Poole and Poole, 2006).

FMASE maintains the advantages of conventional Soxhlet extraction while

overcoming the limitations, such as the long extraction time, non-quantitative extraction of

strongly retained analytes and unsuitability for automation. Solvent distillation in FMASE is

achieved by electrical heating, which is independent of the extractant polarity, and recycling

saves 75-85% of the total extractant volume. The main drawback in FMASE is the difficulty

of using water as extractant due to its design, as both thermal insulation and shortening of the

34
present distillation device is mandatory for reception of water vapour on the sample-cartridge

vessel, condensation there and dropping on the sample. A comparison between conventional

Soxhlet and FMASE for leaching of PAHs, herbicides and n-alkanes from soil shows the

advantages of the latter when compared with the conventional design. FMASE provides

efficiencies similar to those obtained by conventional Soxhlet with extraction times at least

eight times shorter (Fromberg et al., 2006).

35
3.0 CONCLUSION

In Industries Extraction process plays a key role in separation of desired components

from its mixture using a suitable solvent. Extraction has great applications in almost all

industries such as Chemical, Pharmaceuticals, Effluent treatment, Polymer, Petroleum,

Petrochemicals, Food, Metal, Inorganics, Nuclear, etc, so it difficult for any process to occur

without extraction process.

36
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