review article status of the reactive extraction as a...

Review ArticleStatus of the Reactive Extraction as a Method of Separation

Dipaloy Datta1 Sushil Kumar2 and Hasan Uslu3

1Chemical Engineering Department Thapar University Patiala 147004 India2Department of Chemical Engineering Motilal Nehru National Institute of Technology (MNNIT)Allahabad Uttar Pradesh 211004 India3Chemical Engineering Department Engineering and Architecture Faculty Beykent University Ayazaga 34437 Istanbul Turkey

Correspondence should be addressed to Hasan Uslu hasanuslugmailcom

Received 7 August 2014 Accepted 20 September 2014

Academic Editor Saeid Azizian

Copyright copy 2015 Dipaloy Datta et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The prospective function of a novel energy efficient fermentation technology has been getting great attention in the past fifty yearsdue to the quick raise in petroleum costs Fermentation chemicals are still limited in the modern market in huge part becauseof trouble in recovery of carboxylic acids Therefore it is needed considerable development in the current recovery technologyCarboxylic acids have been used as the majority of fermentation chemicals This paper presents a state-of-the-art review on thereactive extraction of carboxylic acids from fermentation brothsThis paper principally focuses on reactive extraction that is foundto be a capable option to the proper recovery methods

1 Introduction

Liquid-liquid extraction (LLE) is a process in which a par-ticular solute is removed from a liquid phase (feed phase) byanother liquid phase (solvent or extract phase) Applicationof extraction in life science started in way back to about3500 BC to recover products from various natural resourcesAt a Sumerian text dated 2100 BC production of perfumespharmaceutical oils andwaxes was documented Inmedievalages extraction was performed with ethanol and was appliedin the field of hydrometallurgy by making use of mineralacids [1] With the developments in thermodynamics par-ticularly the distribution law by Nernst in 1891 and design ofan apparatus for extraction significant improvements wereaccomplished in the late 19th century However it was notuntil the early 1930swhen the first large-scale LLEprocesswasin operation Lazar Edeleanu (a Romanian Chemist 1861ndash1941) removed aromatic and sulphur compounds from liquidkerosene by the LLE process using liquid sulphur dioxide asa solvent at temperature as low as minus6 to minus12∘C This yieldedclean kerosene suitable to be used as a fuel for residentiallighting Nowadays besides the extraction of almost allmetals in mining industries and environmental applicationsextractants are widely used in the extraction of organic

and inorganic acids organic chemistry intermediates andpharmaceuticals for the purposes of separation purificationor enrichment [2] of the product

The main difference between reactive extraction andsolvent extraction is the reaction between the extractantand the solute in the organic phase Aliphatic amines andphosphoric solvents are proposed as effective extractants byearlier researchers [3] While extractants play the major rolein the reaction diluents also have a significant effect onthe level of extraction Nonaromatic water immiscible andpolar solvents with intermediate molecular weights and highboiling points are commonly preferred for the extractionto have high distribution and selectivity [4] The solvents(diluents) control the physical properties (viscosity densitysurface tension etc) of the solvent phase and also affect thestability of the complex structure formed between the soluteand the extractant

The reactive extraction is found to be a promisingmethodfor the recovery of the carboxylic acids from a dilute fermen-tation broth [5ndash10] This separation method has advantagessuch as the following

(i) effective at high concentration of substrate in theextractive fermentation

Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 853789 16 pageshttpdxdoiorg1011552015853789

2 Journal of Chemistry

(ii) the acid can be reextracted and the solvent can bereused

(iii) better control of pH in the bioreactor(iv) better recovery of acid with higher product purity(v) reduction of downstream processing load and recov-

ery cost(vi) reactants are relatively immiscible(vii) product(s) undergoes subsequent undesired reac-

tions in reaction phase(viii) reaction products to be separated are immiscible with

the reaction phase(ix) phase equilibrium can be positively influenced(x) heat transfer is to be improved during the reaction(xi) product-catalyst separation can be affected by a

liquid-liquid separation

Kertes and King [3] categorize the extractants as threemajor types

(i) carbon bonded oxygen bearing extractants(ii) phosphorus bonded oxygen bearing extractants(iii) high molecular weight aliphatic amines

The first two categories are nonreactive in nature andextract the acid molecules by solvation The distinctionbetween the first two categories is based on the strengthof the solvation bonds and the specificity of solvation Thecoordinate bonds between carbon bonded oxygen donorextractant and the acid are too weak for a specific solvationbut it is significantly more for phosphorus bonded oxygenbearing extractants The extractants in the second categorymake the solvation process more specific and the numberof solvating molecules per extracted acid molecule can beaccessible experimentally The aliphatic amines in the thirdcategory can react with the carboxylic acid molecule andform acid-amine complexes by proton transfer or by ion pairformation This causes a significant increase in the distribu-tion coefficient of the carboxylic acid [11] Among aliphaticamines primary alkyl amines are observed to be excessivelysoluble inwater at room temperature while secondary aminesform a gel phase (third phase) at the interface which createdifficulty in phase separation [3]The extractability of tertiaryamines is found to be more than that of the primary andsecondary amines [5] Aliphatic tertiary amines having morethan six carbon atoms per chain are found to be effectiveextractants for the recovery of carboxylic acids [3]

Although a tertiary amine has good extractability itmust always be used with a diluent due to its viscous andcorrosive nature Further the stability of the formed acid-amine complexes in the reactive extraction is affected by thebasicity of the amine which can be manipulated by usingdifferent types of diluents Moreover use of a diluent controlsthe physical properties such as density viscosity and surfacetension of the organic phase [12]

Diluents can be broadly divided into two groups (i)active diluents and (ii) inactive diluents Generally the active

diluents are polar in nature due to the presence of functionalgroups They are good solvating media for an ion-pairsuch as an acid-amine complex [13] The category includeschlorinated hydrocarbon ketone alcohol and halogenatedaromatic solvents Inactive diluents being nonpolar providevery low distribution of the acid and poor solvation of thepolar complexes Alkanes benzene alkyl substituted aromat-ics and so forth fall in this category These diluents limit theformation of the third phase at higher concentrations of acidin the organic phase and are useful in the stripping of acidThe equilibrium curve can be shifted towards the aqueousphase by increasing the concentration of the inert diluent inthe mixture of diluents [14]

Reactive extraction represents a reaction between the acid(solute) and extractant molecule at the interface of aqueousand organic phase where transfers of acid molecules takeplace by the diffusion and solubilizationmechanism Reactiveextraction strongly depends on various parameters suchas aqueous phase composition organic phase compositiontypes of complexes (1 1 2 1 etc) formed properties of thesolvent (extractant and diluent) type of solvent temperatureand pH [15] The purpose should be achieving a highdistribution coefficient with higher selectivity This can berealized by utilizing an appropriate organic phase at optimumconditions

There are two stages in extractive separation (Figure 1)The first is the extraction of the solute to produce a solute-extractant complex and a relatively solute free aqueousraffinateThe second step is necessary for stripping the solutefrom the organic complex to obtain amine free aqueous soluteas a product and also for simultaneously regenerating theextractant recycled back to the extraction unit In the secondstage of reactive extraction it is necessary to regenerate theorganic phase Tamada and King [16] have described twoapproaches for the regeneration of extractant-diluent system(i) temperature swing regeneration and (ii) diluent swingregeneration Yabannavar and Wang [17] have purified lacticacid from a loaded organic phase using sodium hydroxide(NaOH) and hydrochloric acid (HCl) Poole and King [18]have used an aqueous solution of lowmolecular weight aminefor complete regeneration of organic phase

Reactive extraction has many applications in chemicaland pharmaceutical industries (intermediates organic acidsvitamins ) or in hydrometallurgical and environmentalscience (heavy metals inorganic acids ) The liquid ionexchangers are used to promote a certain reaction to accom-plish very selective separations [19] There are many liquidion exchangers commercially available They work basicallywith three different types of mechanisms anion exchangecation exchange and solvation It is practical to use ion-exchangers in a diluent which is immiscible with water sincethey are highly viscous or solid materials The diluent makesthe organic phase easier to handle [1]

There are a significant number of studies on reactiveextraction of organic acids in the literature These studiesinvestigate various aspects of reactive extraction of organicacids chemical interactions between acids and extractantsreaction mechanisms type of extractants and diluents effectof temperature and pH effect of aqueous and organic phase

Journal of Chemistry 3

Aqueous phase Organic phase Stripping phase

Extraction Back-extraction

HCaq + H2O HCorg + S (HCndashS)org HC + stripping agent

HCaq HCorg

Cminus

aq + H3O+

Figure 1 Schematic representation of the reactive extraction process (extraction and back-extraction)

compositions on extraction effect of modifiers extractivefermentation processes kinetics of extraction stripping theacid from the organic phase and so forth

2 Equilibrium Studies on Reactive Extractionof Carboxylic Acids

Several researchers [3 8 9 13 16 21 26 31 56ndash59] havestudied theoretical and experimental aspects of the recoveryof carboxylic acids from their aqueous solutions by reactiveextraction In their work the investigators have examinedthe effects of various parameters on the distribution of theacid (solute) between the aqueous and organic phase Someof these parameters are concentration and composition ofboth phases types of the extractants and diluents pH ofthe aqueous phase temperature of the system and toxicityof the solvent phase to the microorganism [3 13 57 6061] In addition to these experimental studies the possiblereaction mechanisms are also described and determinedusing different equilibrium and kinetic models [8 9 5052] Some experimental results have showed synergistic andantagonistic effects on the extraction of the carboxylic acidswhen there is more than one acid in the aqueous phaseor more than one extractant in the organic phase [21 6263] Some researchers have tried to recover the carboxylicacids from production medium by extractive fermentationand studied the process conditions affecting recovery duringproduction [57 60 61 64]

King and his group have performed the pioneeringstudies on the equilibriumof reactive extraction of carboxylicacids Besides carboxylic acids they have also studied theextraction of chlorinated hydrocarbons and aromatics [65]ethanol [66] ammonia [67] and low molecular weightaliphatic alcohols [3] from aqueous solutions In one of theirearlier work Wardell and King [11] studied the extractionof acetic and formic acids from their aqueous solutions[11] using phosphoryl solvents (tributyl phosphate dibutylphosphonate tributylphosphineoxide and triphenylphos-phineoxide) and tertiary amine extractants (tri-119899-octylamineand tri-iso-octylamine) dissolving in different solvents Highdistribution coefficients are achieved with phosphoryl com-pounds which act as a Lewis base (presence of the phosphorylbond PndashO) The results indicated that with the increasein the electronegativity a decrease in the electron-donatingability and disappearance of Lewis basicity were observedThis study also showed the advantage of using long chainamines as extractants in the recovery of carboxylic acids It

was also observed that the extent of the extraction of aceticacid appeared to increase with an increase in the solubilityparameter of the diluent besides the polarity

At the later stage Kertes and King [3] in 1986 pub-lished a research article in which the authors discussed theimprovements in fermentation technology and its need ofcommercialization They have reviewed 11 carboxylic acids(propionic pyruvic lactic succinic fumaricmaleic itaconictartaric citric and isocitric) which are obtained by aerobicfermentation of glucose via the glycolytic pathway andglyoxylate bypass The investigators pointed out that it is theundissociated part of a monocarboxylic acid which can onlybe extracted into carbon-bonded and phosphorus-bondedsolvent This revealed that the initial pH of the aqueous solu-tion and the dissociation constant (p119870

119886) of the acid are two

very important and influential parameters in the extractionof particular acid Mass action law and Nernst distributionlaw are used in order to evaluate the data The authors haveconsidered the dimerization of acids in the organic phaseand proposed a relation between dimerization constant andpartition coefficient The emphasis is given for the use ofaliphatic tertiary amines compared to primary and secondaryamines In particular monocarboxylic acids under compara-ble conditions are noted to be more easily extracted with anappropriate organic phase than di- or tri-carboxylic acids [3]

King and his coworkers [13 16 56] continued theirstudies on reactive extraction of carboxylic acids In their firststudy [13] they have carried out the extraction equilibriumexperiments of carboxylic acids (acetic lactic succinic mal-onic fumaric and maleic) with different p119870

119886values They

have studied the effect of p119870119886of the corresponding acid

on the extent of extraction It is found that the acid withhigher p119870

119886value is extracted inmore amounts Furthermore

they have also searched for the effect of functional groupspresent in acid other than the primary carboxyl groupon extraction The reactive extraction is examined usingAlamine 336 dissolved in various diluents (active diluents1-octanol DCM chloroform MIBK nitrobenzene inertdiluent heptane) These diluents are selected with differentchemical characteristics such as electron donating electronaccepting polar and nonpolar in order to observe the effect ofdiluent-complex interactions on the equilibrium conditionsand the possible formation of acid-amine complexes (1 12 1) They have indicated that solubility of the acid-aminecomplex in the solvent phase is decreased in the followingorder alcoholge nitrobenzenege proton donating halogenatedhydrocarbon gt ketone gt halogenated aromatic gt benzene gtalkyl aromatic gt aromatic hydrocarbon


In their second study Tamada and King [56] have inves-tigated the chemical interactions between the componentsby using the results of mass action law analysis and thespectroscopic studies Organic phase is analyzed by infraredspectroscopy to examine the stoichiometry of the acid-aminecomplex They emphasize that there is an ion pair formationbetween the amine and first acid molecule and there is ahydrogen bond formation between the carboxyl of the secondacidmolecule and the carboxylate of the first in the formationof 2 1 complex of acid-amine

In the last part of the study [16] this group has carriedout the coextraction of water with the acids by Alamine 336dissolved in various diluents and found that amine had noeffect on the coextraction of water Water coextraction wasdecreased in the order of 1-octanol gt MIBK gt nitrobenzenegt methylene chloride gt chloroform gt heptane during theextraction of succinic acid Coextraction of water for differentacids is also compared and it is revealed that monocarboxylicacids carry less water than dicarboxylic acids In this studythe effect of the temperature on the reactive extractionof carboxylic acids by Alamine 336 is performed It isobserved that the distribution coefficient decreased withthe increase in the temperature of the system as with theformation of the complex the system became more orderedand entropy decreased Consequently the amount of acidextracted decreased with the increase in temperature FinallyKing and his coworkers regenerated the extractant throughback-extraction by two approaches swing temperature andswing diluent methods

The quaternary amines are first studied by Yang et al[68] They have investigated Alamine 336 and Aliquat 336quaternary amine produced by the methylation of Alamine336 and composed of a large organic cation with a chlorideion dissolved in kerosene or 2-octanol to extract lactic aceticand propionic and butyric acids It has been reported thatwhile Alamine 336 can extract only the undissociated acidAliquat 336 can extract both dissociated and undissociatedacids and always gives higher distribution coefficients thanAlamine 336 at all pH values It is also reported in this studythat the extraction power of Alamine 336 is increased by thepolar diluent 2-octanol On the other hand a diluent effectcould not be detected on the extraction power of Aliquat 336

Prochazka et al [69] have studied trialkylamine a mix-ture of straight chain tertiary amine with 7ndash9 carbon atomsdissolved in themixture of 1-octanol and n-heptane to extractlactic malic and citric acids It is reported that all systemsused in this study are sensitive to temperature and solventcomposition In another study Juang et al [21 70] useda tertiary amine based extractant tri-n-octylamine (TOA)dissolved in xylene to extract succinic and tartaric acids[21 70] They obtained thermodynamic data on extractionand compared extraction equilibria of succinic and tartaricacids with TOA dissolved in xylene They have reported thatthe equilibrium distribution coefficient of the acids extractedwith TOA increases with initial concentration of amine in theorganic phase and of the acid in the aqueous phase TOA hasalso been investigated by Poposka et al [71] as an extractantdissolved in an iso decanoln heptane mixture for extractionequilibria of citric acid The data were obtained as a function

of acid amine and isodecanol concentrations at 298K and anappropriate mathematical model was proposed

Most of the studies on reactive extraction in the literatureare focused on a single acid in the aqueous phase HoweverJuang et al [70] have reported that extraction characteristicsare affected by the presence of more than one acid in theaqueous phase Separation mechanisms of lactic and citricacids in the aqueous phase with TOA dissolved in xylenehave been investigated via the supported liquid membranetechnique They have reported large synergistic effects com-pared to single acid systems for low initial concentrationratio of citric to lactic acid (120572) and an antagonistic effectat 120572 = 2 The presence of the second acid has a positiveeffect on the transport of citric acid but a negative effecton that of the lactic acid Transport rate of the acids alsoincreases with TOA concentration and temperature Newsynergistic extraction system for organic acids was developedby Matsumoto et al [72] The extraction equilibria wereinvestigated for acetic glycolic propionic lactic succinicfumaric malic and itaconic acids by tri-n-octylamine (TOA)andor tri-n-butylphosphate (TBP) dissolved in hexane Itis reported that when a mixture of extractants are used asynergy is developed and a more effective extraction of allorganic acids is achieved

The above studies clearly show that the reaction betweenthe extracted acid and the extractant present in the organicphase is dependent on the corresponding acid and the con-tents of the organic phase To explore the possibilities of reac-tive extraction and its application and commercializationfurther studies are carried out with different carboxylic acidsusing various extractants dissolved in different categoriesof diluents A brief review of these extraction studies issummarized in a tabular form and shown in Table 1 to have aclear understanding of the various reactive systems used

21 EquilibriumModels The theories of equilibria of reactiveextraction are explained in this section The model describesthe physical and chemical phenomena occurring in theextraction process in the mathematical forms They alsoexplain interaction mechanism between the components ofaqueous (acid and water) and organic (extractant andordiluent) phases In these model equations assumption ismade that all the reactions are in thermodynamic equilibriumoccurring at the interface of aqueous and organic phases

211 Mass Action Law Model Equilibrium data are inter-preted byMass Action Law which was proposed by GuldbergandWaage in 1864 Kertes and King in 1986 [3] applied MassAction Law for reactive extraction of carboxylic acids Inthe Mass Action Law model activities of the aqueous andorganic phase species are assumed to be proportional to therespective concentration of the species and the equilibriumconstant takes care of the constant of proportionality or thenonidealities associated with the reactive system Thereforethe apparent equilibrium constant (written in terms of speciesconcentration) is used for the development of mathematicalmodel of the reaction equilibrium This model can be sub-categorized in two types (i) physical extraction where only


Table1Ex

tractantdilu

entsystem

forthe

recovery

ofcarboxylicacid

byreactiv

eextraction

equilib

rium

studies

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

1Differentcarbo

xylic

acids

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofcarboxylicacids

[3]

2Lacticacid

TOA

Hexane

Type

ofacid

andinitialacid

concentration

Hydroph

obicity

ofthea

cid

controlsequilib

rium

constants

[20]

3Ac

eticlactic

succinic

malon

icfum

aricand

maleic

Tri-a

lkylam

ine(Alamine3

36)

Methylisobu

tylketon

e(MIBK)

n-heptanedichloromethane

(DCM

)andnitro

benzene

Effectsof

diluent-c

omplex

interactions

Equilib

rium

constantspartition

coeffi

cientand

dimerization

constant

determ

ined

[13]

4Citric

Alamine3

36119901-Xylenetoluenebenzene

MIBK

1-octanolD

CMand

chloroform

Effecto

fdilu

ents

119870

11

11987012

and119870

23

arec

orrelated

with

solvatochrom

icparameters

[12]

6Lactic

TOA

Xylene

TemperatureacidandTO

Aconcentration

(11)(12)and(31)a

cid-TO

Acomplexes

form

ed[21]

7(L+)

lactic

Tri-p

ropylamine(TP

A)a

ndTO

A1-o

ctanolandheptane

Acid

andam

inec

oncentratio

nMixed

tertiary

amineo

fsho

rtandlong

chaincanfacilitatee

asy

phases

eparation

[22]

8Citriclacticand

malic

Tri-iso-octylam

ine(TIOA)

1-octanolandheptane

Effecto

fmod

ifier

andtype

ofacid

Extractio

nmechanism

isprop

osed

consideringph

ysical

andchem

icalextractio

n[23]

9Glyoxylicglycolic

acrylicand

benzoic

Tri-a

lkylph

osph

ineo

xide

(TRP

O)

Kerosene

Aqueou

sand

organicp

hase

compo

sitions

Equilib

rium

mod

elfor11987011

isprop

osed

[24]

10Prop

ionic

Aliq

uat336

Cyclo

hexanehexanetoluene

MIBK

ethylacetatehexane+

MIBK

hexane

+tolueneand

MIBK+toluene

Effecto

fdilu

entand

diluent

mixtureacidandam

ine

concentration

Order

ofextractio

nethylacetate

gtMIBKgtMIBK+toluenegt

toluenegt

hexane

+MIBKgt

toluene+

hexanegtcyclo

hexane

gthexane

[25]

11Prop

ionic

Tri-119899

-butylph

osph

ate(TB

P)

TOAand

Aliq

uat336

1-Octanol

Acid

andextractant

concentration

Order

ofextractib

ilityisfoun

dto

beTO

AgtAliq

uat336gtTB

P11

complex

form

ed[26]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

12Ita

conicmaleicmalic

oxalictartaric

and

succinic

TBP

Do-decane

pHandinitialacid

concentration

Mechanism

ofdi-carbo

xylic

acidsisp

ropo

sed

[27]

13Nicotinic

TOPO

andTB

P

Benzeneheptanekerosene

1-octanolM

IBK

diethylether

decanekerosene+

1-octanol

andheptane+

1-octanol

Effecto

fdilu

entextractant

type

initialacidand

extractant

concentration

Solvationnu

mbera

ndequilib

rium

extractio

nconstants

ared

etermined

[28]

14Levulin

ic119899-Lauryltri-

alkyl-m

ethylamine

(AmberliteLA

-2)

Dim

ethylphthalatedim

ethyl

adipatedimethylsuccinate

dimethylglutaratediethyl

carbon

ateiso

amylalcoho

l1-h

exanol1-octanol1-non

anol

1-decanoldiisob

utylketone

(DIBK)

and

MIBK

Dilu

enteffectand

amine

concentration

LSER

mod

elprop

osed

and119870

11

119870

21

and119870

31

ared

etermined

[29]

15Fo

rmic

AmberliteLA

-2

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanolD

IBK

andMIBK

Effecto

fdilu

entand

amine

concentration

Extractio

nconstants(119870

51

11987061

and119870

71

)wered

etermined

and

LSER

mod

elprop

osed

[30]

16Nicotinic

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofnicotin

icacid

[31]

17Glycolic

AmberliteLA

-21-O

ctanolcyclohexane

iso-octanetoluene2-octano

ne

andMIBK

Solventtypeam

inea

ndacid

concentration

Order

ofextractio

nMIBKgt

2-octano

negt1-o

ctanolgttoluene

gtiso

-octanegt

cyclo

hexane

[32]

18Citric

Tri-d

odecylam

ine(TD

DA)a

ndAmberliteLA

-2

MIBK

1-octanoltoluene

cyclo

hexane1-octanol+toluene

1-octanol+MIBK

MIBK+

toluene1-o

ctanol+toluene

1-octanol+MIBK

MIBK+

tolueneandiso

-octane

Dilu

enteffectaminea

ndacid

concentration

1-Octanolprop

osed

tobe

most

effectiv

esolvent

[33]

19Glutaric

TOA

Isoamylalcoho

l1-o

ctanol

1-non

anol1-decanolm

ethyl

ethylketon

e(MEK

)diiso

butyl

ketone

(DIBK)

hexan-2-one

toluenekeroseneand

hexane

Dilu

enteffectaminea

ndacid

concentration

Kerosene

isfoun

dto

bethem

ost

effectiv

edilu

entEq

uilib

rium

constantsfor

11and

21

complex

aree

stim

ated

[34]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

20Lactic

TBP

Dod

ecane

Acid

andsolventcom

position

change

inthep

hase

volumes

and

pH

Apparent

equilib

rium

constants

andthen

umbero

freacting

extractant

molecules

[35]

21Ac

rylic

AmberliteLA

-2Cy

clohexane2-octanon

etolueneMIBK

iso-octane

hexaneand

1-octanol

Type

ofdiluentandam

ine

concentration

11amp

12acid-aminec

omplexes

forp

roton-do

natin

gdiluentsand

11amp

23for

non-proton

-don

atingdiluents

overallextractionconstants(119870

11

119870

12

and119870

23

)

[36]

22Fo

rmic

TDDAandTB

PEthylvaleratediethyladipate

diethylsebacate1-o

ctanoland

heptane

Effecto

fdilu

entacid

andam

ine

concentration

Com

parativ

estudy

ofph

ysical

andchem

icalextractio

nTD

DA

suggestedto

betheb

est

extractant

[37]

23PenicillinG

Di-119899

-octylam

ineTO

AN

235(a

mixture

oftertiary

amines)TB

Panddi-(2-ethylhexyl)p

hospho

ricacid

(D2E

HPA

)

n-Bu

tylacetateM

IBK

2-ethyl

hexano

lkeroseneand

heptane

Initialacid

concentration

pHandtemperature

Effecto

fextractanto

nthe

stabilityof

penicillinGmainly

depend

sontemperature

degradationof

penicillinGin

alkalisolutio

nisgoverned

bypH

mechanism

ofdegradation

discussed

[38]

24Succinic

AmberliteLA

-2Hexanecyclo

hexanetoluene

iso-octaneMIBK

2-octano

ne

and1-o

ctanol

Initialextractant

concentration

Extractio

nconstants(1112amp

23)

foun

dou

tordero

fextractio

nof

diluents

1-octanol

gt2-octano

negtMIBKgttoluene

gtiso

-octanegt

hexanegt

cyclo

hexane

[39]

25Ita

conic

TBPandAliq

uat336

Sunfl

ower

oil

Initialacid

andextractant

concentration

Non

toxics

ystem

prop

osed

[40]

26Prop

ionic

TBP

Kerosene

and1-d

ecanol

Aqueou

sand

organicp

hase

compo

sitionsand

temperature

Mod

ifier

hasa

stron

geffecto

ndegree

ofextractio

n[41]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

27L(+)T

artaric

AmberliteLA

-21-o

ctanolcyclohexane

isooctanehexaneandMIBK

Organicph

asec

ompo

sitions

Extractabilityof

acid

ishigh

especiallywith

polarsolvents

(MIBKand1-o

ctanol)

[42]

28Ca

proic

TBP

MIBKandxylene

Phasec

ompo

sitions

MIBKisab

ettersolvent

than

xylene

[43]

29Ac

etic

TOA

DCM

butylacetateheptanes

and1-o

ctanol

Organicph

asec

ompo

sitions

and

pH

Thes

olvent

polaritycontrolsthe

form

edstr

ucture

ofthe

interfa

cialacid

andTO

Acompo

unds

[44]

30Picolin

icTB

PSunfl

ower

andcasto

roil

Aqueou

sand

organicp

hase

compo

sitions

Differentm

odels

areu

sedto

representthe

equilib

rium

data

[45]

31Picolin

icTrialkylam

ine(N235)T

BPTetrachlorom

ethanekerosene

and1-o

ctanol

Aqueou

sand

organicp

hase

compo

sitionsand

pH

Distrib

utioncoeffi

cienth

ighly

depend

ento

npH

andthe

apparent

alkalin

ityof

N2351-o

ctanol

[46]

32Ac

eticpropion

ic

butyric

andvaleric

TBP

Cyclo

hexanesulfonated

keroseneand

1-octanol

Equilib

rium

timetemperature

andph

aser

atio

Con

ditio

nsof

extractio

nand

strip

ping

arefou

nd[47]

33Citric

TOA

Rice

bran

oilsunfl

ower

oil

soybeanoilandsesameo

ilAq

ueou

sand

organica

ndph

ase

compo

sitions

Overallextractio

nconstantsa

ndassociationnu

mbers

[48]


diluent (pure form) is used for extraction and (ii) chemicalextraction where both extractant (phosphoric and aminic)and diluent take part in the extraction process

(1) Physical ExtractionThe process of physical equilibria withpure diluent takes place in three parts (i) partial dissociationof the acid molecule in aqueous phase (ii) distribution of theundissociated acid molecule between aqueous and organicphases and (iii) dimerization of undissociated acid moleculein the organic phase

(i) Carboxylic acid can exist in undissociated (HC) anddissociated (Cminus) forms in the aqueous solution of water Thedissociation of the acid in the aqueous solution depends uponthe strength of the acid (p119870

119886) and is described by

HClarrrarr H+ + Cminus (1)

The dissociation constant (119870119886) is calculated using

119870

119886=

[H+] [Cminus][HC]

(2)

The total acid concentration in the aqueous phase (119862HC) andundissociated acid [HC] concentration can be expressed as(3) and (4) respectively

119862HC = [HC] + [Cminus] (3)

[HC] =119862HC

(1 + (119870

119886 [H+]))

(4)

(ii) The distribution of the undissociated acid moleculebetween aqueous and organic phases is represented by (5) andthe corresponding partition coefficient is given by (6)

HClarrrarr HC (5)

119875 =

[HC][HC]

(6)

(iii) The undissociated extracted acid molecules candimerize in the organic phase due to the strong donor-acceptor interaction This is due to the solute-solute inter-action through hydrogen bond which is stronger than thesolute-solvent interactionThe dimerization of the undissoci-ated extracted acid in the organic phase (HC) is representedby

2HClarrrarr (HC)2

(7)

The dimerization constant (119863) is expressed by

119863 =

(HC)2

(HC)2

(8)

The extraction efficiency (with pure diluent) of acid iscalculated by the physical distribution coefficient 119870diluent

119863

119870

diluent119863

=

119862

diluentHC

119862

diluentHC

(9)

where 119862diluentHC is the total (undissociated and dimer forms)

concentration of acid in the organic phase and 119862

diluentHC is

the total (dissociated and undissociated) concentration inaqueous phase at equilibrium with pure diluent

For a dilute concentration of acid (as used in this study)119870

diluent119863

in terms of dimerization constant (119863) and partitioncoefficient (119875) can be represented as [3]

119870

diluent119863

= 119875 + 2119863119875

2

[HC] (10)

To estimate the values of physical extraction parameters (119875and119863) the plots of119870diluent

119863

versus [HC] can be fitted linearlyand value of 119875 from the intercept and 119863 from the slope canbe obtained

(2) Chemical Extraction The interaction of acid moleculewith the extractant molecule in the chemical extraction canoccur in two ways (i) through hydrogen bonding of undisso-ciated acid molecule (11) and (ii) by ion pair formation (12)[73]

HC + Slarrrarr (HC) (S) (11)

H+ + Cminus + Slarrrarr H+CminusS (12)

The extractionmechanism described in (11) and (12) dependson the pH of aqueous solution p119870

119886of acid the acid and

extractant concentrations and the basicity of the extractantwith respect to the acid (p119870

119861) The extraction of carboxylic

acid by phosphorous based extractants (TBP TOPO etc) canbe described by (11) and that for amine based extractants(TOA Aliquat 336 etc) by both mechanisms (11) and (12)

An equilibrium extraction process is described as a set ofreactions (see (13)) between 119898molecules of acid (HC) and 119899molecules of extractant (S) to form various (119898 119899) complexeswith corresponding apparent equilibrium constant (119870

119864) as

given by (14)

119898HC + 119899Slarrrarr (HC)119898(119878)

119899

(13)

119870

119864=

[(HC)119898(119878)

119899

]

[HC]119898 [S]119899 (14)

The distribution coefficient (119870119863) can be written as

119870

119863=

119862HC119862HC

= 119898

[(HC)119898(119878)

119899

]

119862HC

(15)

Substituting the values of [HC] and [(HC)119898(119878)

119899

] from (4) and(15) respectively in (14) results in

119870

119864=

119870

119863(1 + 119870

119886 [H+])119898

119898119862

119898minus1

HC [S]119899

(16)

The equilibrium free extractant concentration ([S]) in theorganic phase is represented as

[S] = [S]in minus 119899 [(HC)119898(S)119899

] (17)

[S] = [S]inminus

119870

119863119899119862HC119898

(18)


Now putting the value of [S] from (18) in (16) (19) is derived

119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)

The values of equilibrium extraction constant (119870119864) and the

stoichiometry (119898 119899) of the reactive extraction are determinedby minimizing the error between the experimental andpredicted values of119870

119863

The equilibriummodel for the simultaneous formation ofvarious types of acid-extractant complexes (1 1 2 1 3 1 1 2etc) can be represented by a system of equations (see (20)to (23)) depending upon the type of the acid extractant anddiluent and their concentrations used in the experiment


HC + (HC) (S) larrrarr (HC)2(S) (21)

HC + (HC)2(S) larrrarr (HC)

3(S) (22)

(HC) (S) + Slarrrarr (HC) (S)2

(23)

The corresponding extraction constants (11987011 11987021 11987031

and119870

12) are calculated using (24) to (27)

119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C

12are the concentrations of 1 1 2 1 3 1

and 1 2 complexes respectively in the organic phase 119862HCand [S] are given by (28) and (29) respectively

119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)

Using experimental results and by applying the mass actionlaw the values of the individual equilibrium constants (119870

11

119870

21 11987031

and 11987012) and the concentration of complexes (C

11

C21 C31 and C

12) can be estimated An objective function

can be defined to determine individual equilibrium constantsbased on experimental values of 119862HC

Now amodel based on the loading ratio (119885) for formationof various types of complexes (1 1 2 1 etc) between acidand extractant can also be described The extent to whichthe organic phase (extractant and diluent) may be loadedwith acid is expressed by the loading ratio It is a ratio ofacid concentration in the organic phase at equilibrium to theinitial extractant concentration in the organic phase ([S]in)

119885 =

119862HC

[S]in

(30)

The value of 119885 depends on the extractability of the acid(strength of the acid-base interaction) and its aqueous con-centration and the stoichiometry of the overall extractionequilibrium It is found that when the organic phase is nothighly concentrated by acid that is at very low loading ratios(119885 lt 05) 1 1 acid-extractant complex is formed A plot of119885(1 minus 119885) versus [HC] yields a straight line passing throughorigin with a slope of complexation constant (119870

11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)

If the carboxylic acid concentration is high enough (at least119885 gt 05) this relation can be expressed as shown by

119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)

To account for the extraction only by extractant a term isdefined for the distribution of acid by chemical extraction(119870chem119863

) as

119870

chem119863

=

119862HC minus ]119862diluentHC

119862HC

(33)

where ] is the volume fraction of diluent in the organic phaseTherefore the overall distribution coefficient (119870total

119863

) byphysical and chemical extraction is obtained by adding (9)and (33)

119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)


In general the diluent alone also solvates some amount ofsolute (acid) from aqueous solution by physical extractionwhich is described in the previous sectionTherefore in sucha case expression for [(HC)

119898(S)119899] is represented as

[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)

Therefore (35) could be obtained by including the term forphysical extraction and rewriting (34) as

119870

119898119899[HC]119898 =


[[S]inminus 119899 (119862HC minus ]119862

diluentHC )]

119899 (36)

212 Linear Solvation Energy Relation (LSER) A linearsolvation energy relationship (LSER) approach has beenintroduced by Kamlet et al [74] in 1983 and then improvedby Abraham [75] It characterizes solvation effects in termsof nonspecific and H-bonding interactions Thus a solvationproperty of interest (119883119884119885) for an organic solute is modeledby a linear solvation energy relationship of the form [76]

119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)

where 120575H is the Hildebrandrsquos solubility parameter a measureof the solvent-solvent interactions that are interrupted increating a cavity for the solute 120587lowast an index of solventdipolarity or polarizability measures the ability of the solventto stabilize a charge or a dipole by virtue of its dielectric effect120575 a polarizability correction term equals 00 for nonchlo-rinated aliphatic solvents 05 for polychlorinated aliphaticsand 10 for aromatic solvents Solvatochromic parameter 120573representing scale of solvent HBD (hydrogen-bond donor)acidities describes the ability of solvent to donate a protonin a solvent-to-solute H-bond 120572 scale of HBA (hydrogen-bond acceptor) basicities provides a measure of the solventrsquosability to accept a proton (donate an electron pair) in a solute-to-solvent H-bondThe 120585 parameter a measure of coordinatecovalency equals minus020 for P=O bases 00 for C=O S=OandN=Obases 020 for single-bonded oxygen bases 060 forpyridine bases and 100 for 1199041199013-hybridized amine bases Thecoefficients 119901 119904 119890 119889 119886 ℎ and 119887 are the regression coefficientsthat measure the relative susceptibilities of119883119884119885 to indicatedsolvent property scale Equation (37) is adopted to describethe effect of diluents on the values of distribution coefficients(119870119863)

log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)

where the parameters 120587lowast 120575 120573 and 120572 refer to the diluentsand 119870

119863

0 represents the distribution coefficient for an idealdiluent The fifth term of (38) which contains the solubilityparameter 120575H does not affect the values of the objectivefunction (log

10

119870

119863) significantly and the value of 120585 = 0 is

considered for the diluents used in this study Thus (38)results in

log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)

Equation (39) can be adopted to describe the effect ofdiluents on the values of distribution coefficients (119870

119863) In

case a mixture of diluents is used with the extractantthe solvatochromic parameters of the solvent mixtures arecalculated as [77]

119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)

where 1198831is the mole fraction of the first solvent and 119883

2=

1 minus 119883

1is the mole fraction of the second solvent 119878119875

1is

the solvatochromic parameter of the first solvent and 1198781198752

is the solvatochromic parameter of the second solvent insolvent mixturesThe solvatochromic parameters of differentdiluents can be found in the study by Kamlet et al [74]

22 Kinetic Studies on Reactive Extraction of Carboxylic AcidsKinetic studies are equally essential as equilibrium studies forthe complete design of a reactive extraction unit Lewis typestirred cell [78] cylindrical stirring vessel with highly agitatedsystem [50] stirred cell with a microporous hydrophobicmembrane [79] and so forth were used to perform thekinetic studies on the reactive extraction of various carboxylicacids In these studies the investigators have describedand analyzed the kinetic mechanism of reactive extractionusing formal elementary kinetic model a mechanism ofreactions of acid-amine complexes [50] theory of extractionaccompanied by a chemical reaction [79] and so forth Theestimation of the intrinsic kinetic parameters such as rateconstants (forward and backward) and reaction order werealso carried out using experimental data According to theirfindings the reaction between the acid and the extractantnot only depends on the composition of the organic andaqueous phases it also depends on the hydrodynamic param-eters (volume ratio of phases interfacial area and speed ofagitation) of the system which also confirmed the region ofthe (mass transfer controlled or reaction controlled) reactionIn a study by Jun et al [80] in 2007 it was observed that thereaction rates were affected by pH and contamination presentin the aqueous phase At a pH greater than the p119870

119886of acid

more dissociation took place leading to the reduction in theextraction efficiency Therefore it was recommended thatto have an effective separation of acid from the productionmedia the pH of the fermentation broth should be kept ata value less than the p119870

119886of the acid Further a brief review

of the kinetic studies on reactive extraction is summarized inTable 2 to have an overviewof the reactive kinetics of differentcarboxylic acids

221 Kinetic Model A comprehensive study on the theory ofextraction accompanied with chemical reaction in a stirredcell is proposed by Doraiswamy and Sharma [79] in 1984 todetermine the effect of chemical reaction on the specific rateof reaction With the help of the film and renewal theorieswith physico-chemical and hydrodynamic parameters theyhave classified the reactive system into four reaction regimes(very slow slow fast and instantaneous) depending on theirrelative diffusion and reaction rates (Table 3)

The value of physical mass transfer coefficient (119896119871) is

required to confirm the regime of reaction This is obtained


Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio

nspeedinterfacialareab

etween

twoim

misc

iblesolutio

nspHof

aqueou

sph

aseinitialcarrierandpenicillinG

concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with

theforwardandbackward

rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature

Thefractionalresistanceso

faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere

investigateddiffusionthroug

hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3

36andfirstorderinacid

with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]


Table 3 Classical limiting regimes for irreversible reaction in a stirred cell

Regime Description Hatta Number (Ha) Effect on the specific rate of extraction (molsdotmminus2sdotsminus1)[HC]molsdotLminus1

[119878]

molsdotLminus1Stirrer speed(119873 rpm)

Volume ratio ofphases

1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org

2 Slow 120572[HC] NoneIncreases withincrease in thespeed of stirring

None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None

4 Instantaneous None 120572[119878]

Increases withincrease in thespeed of stirring

None

by conducting physical extraction of acid from aqueous phasewith pure diluent For a batch process a differential massbalance yields the following equation

119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast

org minus 119862org) (41)

where119860119888is the interfacial area (m2)119881aq is the aqueous phase

volume (m3)119862lowastorg is the equilibriumacid concentration in theorganic phase The time-dependent concentration of acid inthe organic phase is obtained by integrating (42) as

ln(119862

lowast

org

119862

lowast

org minus 119862org) =

119896

119871119860

119888

119881org119905 (42)

A plot of ln(119862lowastorg(119862lowast

orgminus119862org)) versus time (119905) yields a straightline and the slope is used to evaluate physical mass transfercoefficient (119896

119871)

The reaction between acid and extractant is reversibleThis problem of reversibility can be avoided by measuringthe initial specific rate of reaction which is governed onlyby the forward reaction Therefore in this study the initialspecific rate of extraction 119877HC0 (molsdotmminus2sdotsminus1) is calculatedfrom experimental data using the following equation

119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)

(119889119862HCorg119889119905)119905=0 is the initial slope of curve which is arepresentation of the concentration in the organic phaseversus time (119905) The values of 119877HC0 are determined withvarious experimental conditions and used to determine theprobable effect of the important variables and to draw aninference on the appropriate kinetics of reactive extractionIn this regard the effects of the speed of agitation (119873)and volume ratio of the phases (119881org119881aq) on the initialspecific rate of extractionmust be examined to determine thereaction regime Therefore based on the guidelines providedby Doraiswamy and Sharma [79] the reactive extraction ofacid with extractant in diluent is governed by the followingequation

119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)

where 1205721015840 and 1205731015840 are the orders of the reaction with respect toacid and extractant respectively and 119896

12057210158401205731015840 is the rate constant

of the reactionFor a (1205721015840 1205731015840) reaction taking place in the organic phase

with a rate law shown in (44) and with a high excessof extractant Hatta number (119867119886) is given by a generalexpression as

119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)

119863HC is the diffusion coefficient of acid into diluentThe valueof 119863HC is estimated using Wilke-Change (1955) and Reddy-Doraiswamy (1967) equations which are given by (46) and(47) respectively

119863HC = 74 times 10minus12

119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)

whereΨ denotes the diluent association factor forall signifies themolar volume of the component 119879 is temperature (K) 119872and 120578 represent molecular weight (kgsdotkmolminus1) and viscosity(kgsdotmminus1sdotsminus1) of the diluent respectively

To determine the effect of reaction on the pure masstransfer of acid from the aqueous to the organic phase theenhancement factor for the reactive extraction of acid iscalculated using

Φ =

119877HC0

119896

119871119862

lowast

org (48)

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

References

[1] H Bart Reactive Extraction Springer Berlin Germany 1stedition 2001


[2] R Marr and H J Bart ldquoSolvent-extractionrdquo Chemie IngenieurTechnik vol 54 no 2 pp 119ndash129 1982

[3] A S Kertes and C J King ldquoExtraction chemistry of fermenta-tion product carboxylic acidsrdquo Biotechnology and Bioengineer-ing vol 28 no 2 pp 269ndash282 1986

[4] C H Holten Lactic Acid Properties and Chemistry of LacticAcid and Derivatives Springer Berlin Germany 1st edition1971

[5] R Wennersten ldquoExtraction of carboxylic acid from fermen-tation broth in using solution of tertiary aminerdquo Journal ofChemical Technology and Biotechnology no 2 pp 85ndash94 1983

[6] J Hartl and R Marr ldquoExtraction processes for bioproductseparationrdquo Separation Science and Technology vol 28 no 1ndash3pp 805ndash819 1993

[7] D Cascaval and A I Galaction ldquoNew separation techniques onbioseparations 1 Reactive extractionrdquo Chemical Industry vol58 no 9 pp 375ndash386 2004

[8] K L Wasewar A B M Heesink G F Versteeg and V GPangarkar ldquoReactive extraction of lactic acid using alamine 336in MIBK equilibria and kineticsrdquo Journal of Biotechnology vol97 no 1 pp 59ndash68 2002

[9] K L Wasewar A B M Heesink G F Versteeg and V GPangarkar ldquoEquilibria and kinetics for reactive extraction oflactic acid using Alamine 336 in decanolrdquo Journal of ChemicalTechnology amp Biotechnology vol 77 no 9 pp 1068ndash1075 2002

[10] S Kumar and B V Babu ldquoProcess intensification for separationof carboxylic acids from fermentation broths using reactiveextractionrdquo Journal of Future Engineering and Technology vol3 pp 21ndash28 2008

[11] J MWardell and C J King ldquoSolvent equilibria for extraction ofcarboxylic acids fromwaterrdquo Journal of Chemical amp EngineeringData vol 23 no 2 pp 144ndash148 1978

[12] V Bızek J Horacek R Rericha and M Kousova ldquoAmineextraction of hydroxycarboxylic acids 1 Extraction of cit-ric acid with 1-octanoln-heptane solutions of trialkylaminerdquoIndustrial amp Engineering Chemistry Research vol 31 no 6 pp1554ndash1562 1992

[13] J A Tamada A S Kertes and C J King ldquoExtraction ofcarboxylic acids with amine extractants 1 Equilibria and lawof mass actionmodelingrdquo Industrial and Engineering ChemistryResearch vol 29 no 7 pp 1319ndash1326 1990

[14] D H Han and W H Hong ldquoReactive extraction of lactic acidwith trioctylaminemethylene chloriden-hexanerdquo SeparationScience and Technology vol 31 no 8 pp 1123ndash1135 1996

[15] E Kahya E Bayraktar and U Mehmeto ldquoOptimization ofprocess parameters for reactive lactic acid extractionrdquo TurkishJournal of Chemistry vol 25 no 2 pp 223ndash230 2001

[16] J A Tamada andC J King ldquoExtraction of carboxylic acids withamine extractants 3 Effect of temperature water coextractionand process considerationsrdquo Industrial and Engineering Chem-istry Research vol 29 no 7 pp 1333ndash1338 1990

[17] V M Yabannavar and D I C Wang ldquoStrategies for reducingsolvent toxicity in extractive fermentationsrdquo Biotechnology andBioengineering vol 37 no 8 pp 716ndash722 1991

[18] L J Poole and C J King ldquoRegeneration of carboxylic acid-amine extracts by back-extraction with an aqueous solution ofa volatile aminerdquo Industrial amp Engineering Chemistry Researchvol 30 no 5 pp 923ndash929 1991

[19] H Bart ldquoFrom single droplet to column designrdquo in Proceedingsof the 6th World Congress of Chemical Engineering MelbourneAustralia September 2001

[20] R S Juang and R H Huang ldquoKinetic studies on lactic acidextraction with amine using a microporous membrane-basedstirred cellrdquo Journal ofMembrane Science vol 129 no 2 pp 185ndash196 1997

[21] R S Juang and R H Huang ldquoEquilibrium studies on reactiveextraction of lactic acid with an amine extractantrdquo ChemicalEngineering Journal vol 65 no 1 pp 47ndash53 1997

[22] Y K Hong and W H Hong ldquoReactive extraction of lacticacid with mixed tertiary amine extractantsrdquo BiotechnologyTechniques vol 13 no 12 pp 915ndash918 1999

[23] G Malmary J Albet A Putranto H Hanine and J MolinierldquoRecovery of aconitic and lactic acids from simulated aque-ous effluents of the sugar-cane industry through liquid-liquidextractionrdquo Journal of Chemical Technology and Biotechnologyvol 75 no 12 pp 1169ndash1173 2000

[24] Y Li Y Wang Y Li and Y Dai ldquoExtraction of glyoxylic acidglycolic acid acrylic acid and benzoic acid with trialkylphos-phine oxiderdquo Journal of Chemical and Engineering Data vol 48no 3 pp 621ndash624 2003

[25] H Uslu and I Inci ldquo(Liquid + liquid) equilibria of the (water +propionic acid + Aliquat 336 + organic solvents) at T = 29815Krdquo Journal of ChemicalThermodynamics vol 39 no 5 pp 804ndash809 2007

[26] A Keshav K L Wasewar and S Chand ldquoExtraction of pro-pionic acid using different extractants (tri-n-butylphosphatetri-n-octylamine and Aliquat 336)rdquo Industrial and EngineeringChemistry Research vol 47 no 16 pp 6192ndash6196 2008

[27] G Kyuchoukov A F Morales J Albet G Malmary andJ Molinier ldquoOn the possibility of predicting the extractionof dicarboxylic acids with tributylphosphate dissolved in adiluentrdquo Journal of Chemical amp Engineering Data vol 53 no3 pp 639ndash647 2008

[28] S Kumar K L Wasewar and B V Babu ldquoIntensification ofnicotinic acid separation using organophosphorous solvatingextractants by reactive extractionrdquo Chemical Engineering andTechnology vol 31 no 11 pp 1584ndash1590 2008

[29] H Uslu S I Kirbaslar and K L Wasewar ldquoReactive extractionof levulinic acid by amberlite LA-2 extractantrdquo Journal ofChemical and Engineering Data vol 54 no 3 pp 712ndash718 2009

[30] H Uslu C Bayat S Gokmen and Y Yorulmaz ldquoReactiveextraction of formic acid by amberlite LA-2 extractantrdquo Journalof Chemical and EngineeringData vol 54 no 1 pp 48ndash53 2009

[31] S Kumar and B V Babu ldquoExtraction of pyridine-3-carboxylicacid using 1-dioctylphosphoryloctane (TOPO) with differentdiluents equilibrium studiesrdquo Journal of Chemical and Engi-neering Data vol 54 no 9 pp 2669ndash2677 2009

[32] Y S Asci and I Inci ldquoExtraction of glycolic acid from aqueoussolutions by amberlite la-2 in different diluent solventsrdquo Journalof Chemical and Engineering Data vol 54 no 10 pp 2791ndash27942009

[33] S S Bayazit H Uslu and I Inci ldquoComparative equilibriumstudies for citric acid by amberlite LA-2 or Tridodecylamine(TDA)rdquo Journal of Chemical amp Engineering Data vol 54 no7 pp 1991ndash1996 2009

[34] N Pehlivanoglu H Uslu and S I Kirbaslar ldquoExperimentaland modeling studies on the extraction of glutaric acid bytrioctylaminerdquo Journal of Chemical and Engineering Data vol54 no 12 pp 3202ndash3207 2009

[35] A Labbaci G Kyuchoukov J Albet and J Molinier ldquoDetailedinvestigation of lactic acid extraction with tributylphosphatedissolved in dodecanerdquo Journal of Chemical and EngineeringData vol 55 no 1 pp 228ndash233 2010


[36] Y S Asci and I Inci ldquoExtraction equilibria of acrylic acidfrom aqueous solutions by amberlite LA-2 in various diluentsrdquoJournal of Chemical and Engineering Data vol 55 no 7 pp2385ndash2389 2010

[37] S Sahin S S Bayazit M Bilgin and I Inci ldquoInvestigationof formic acid separation from aqueous solution by reactiveextraction effects of extractant and diluentrdquo Journal of Chemicalamp Engineering Data vol 55 no 4 pp 1519ndash1522 2010

[38] Z Ren W Zhang J Li S Wang J Liu and Y Lv ldquoEffect oforganic solutions on the stability and extraction equilibrium ofpenicillin Grdquo Journal of Chemical and Engineering Data vol 55no 8 pp 2687ndash2694 2010

[39] Y S Asci I Inci and H Uslu ldquoLSER modelim extraction ofsuccinic acid by tridodecyl amine dissolved in 2-octanone and1-octanlolrdquo Journal of Industrial and Engineering Chemistry vol32 pp 1951ndash1957 2010

[40] K L Wasewar D Shende and A Keshav ldquoReactive extractionof itaconic acid using tri-n-butyl phosphate and aliquat 336in sunflower oil as a non-toxic diluentrdquo Journal of ChemicalTechnology and Biotechnology vol 86 no 2 pp 319ndash323 2011

[41] S Kumar D Datta and B V Babu ldquoDifferential evolutionapproach for reactive extraction of propionic acid using tri-n-butyl phosphate (TBP) in kerosene and 1-decanolrdquo Materialsand Manufacturing Processes vol 26 no 9 pp 1222ndash1228 2011

[42] I Inci Y S Asci and A F Tuyun ldquoReactive extraction of L (+)tartaric acid by amberlite LA-2 in different solventsrdquo E-Journalof Chemistry vol 8 supplement 1 pp S509ndashS515 2011

[43] K L Wasewar and D Shende ldquoEquilibrium study for reactiveextraction of caproic acid in MIBK and Xylenerdquo Engineeringvol 3 pp 829ndash835 2011

[44] D Cascaval L Kloetzer and A-I Galaction ldquoInfluence oforganic phase polarity on interfacial mechanism and efficiencyof reactive extraction of acetic acid with tri-n-octylaminerdquoJournal of Chemical amp Engineering Data vol 56 no 5 pp 2521ndash2526 2011

[45] M D Waghmare K L Wasewar S S Sonawane and D ZShende ldquoNatural nontoxic solvents for recovery of picolinicacid by reactive extractionrdquo Industrial amp Engineering ChemistryResearch vol 50 no 23 pp 13526ndash13537 2011

[46] L Zhang F Yu Z Chang Y Guo and D Li ldquoExtraction equi-libria of picolinic acid with rrialkylaminen-octanolrdquo Journal ofChemical and Engineering Data vol 57 no 2 pp 577ndash581 2012

[47] Y-P Ren J-J Wang X-F Li and X-H Wang ldquoReactiveextraction of short-chain fatty acids from synthetic acidicfermentation broth of organic solid wastes and their strippingrdquoJournal of Chemical amp Engineering Data vol 57 no 1 pp 46ndash512012

[48] A Keshav P Norge and K L Wasewar ldquoReactive extraction ofcitric acid using tri-n-octylamine in nontoxic natural diluentspart 1mdashequilibrium studies from aqueous solutionsrdquo AppliedBiochemistry and Biotechnology vol 167 no 2 pp 197ndash213 2012

[49] S S Wang and C J Lee ldquoKinetics of penicillin G extractionby Amberlite LA-2 as a mobile carrier in a constant-interface-area cellrdquo Chemical Engineering Journal and the BiochemicalEngineering Journal vol 58 no 3 pp 285ndash290 1995

[50] F A Poposka K Nikolovski and R Tomovska ldquoKineticsmechanism and mathematical modelling of extraction of citricacid with isodecanoln-paraffins solutions of trioctylaminerdquoChemical Engineering Science vol 53 no 18 pp 3227ndash32371998

[51] R-S Juang and Y-S Lin ldquoInvestigation on interfacial reactionkinetics of Penicillin G and Amberlite LA-2 from membrane

flux measurementsrdquo Journal of Membrane Science vol 141 no1 pp 19ndash30 1998

[52] F A Poposka J Prochazka R Tomovska and A GrizoldquoExtraction of tartaric acid from aqueous solutions with tri-iso-octylamine (HOSTAREXA 324) Equilibrium and kineticsrdquoChemical Engineering Science vol 55 no 9 pp 1591ndash1604 2000

[53] M Hironaka M Hirata H Takanashi T Hano and S MiuraldquoKinetics of lactic acid extraction with quaternary ammoniumsaltrdquo Separation Science andTechnology vol 36 no 13 pp 2927ndash2943 2001

[54] H K Gaidhani K L Wasewar and V G Pangarkar ldquoIntensifi-cation of enzymatic hydrolysis of penicillin G Part 1 Equilibriaand kinetics of extraction of phenyl acetic acid by Alamine336rdquoChemical Engineering Science vol 57 no 11 pp 1979ndash19842002

[55] S C Lee ldquoKinetics of reactive extraction of Penicillin G byAmberlite LA-2 in kerosenerdquo AIChE Journal vol 50 no 1 pp119ndash126 2004

[56] J A Tamada andC J King ldquoExtraction of carboxylic acids withamine extractants 2 Chemical interactions and interpretationof datardquo Industrial and Engineering Chemistry Research vol 29no 7 pp 1327ndash1333 1990

[57] Y Tong M Hirata H Takanashi T Hano M Matsumotoand S Miura ldquoSolvent screening for production of lactic acidby extractive fermentationrdquo Separation Science and Technologyvol 33 no 10 pp 1439ndash1453 1998

[58] A Keshav S Chand and K L Wasewar ldquoEquilibrium studiesfor extraction of propionic acid using tri-n-butyl phosphate indifferent solventsrdquo Journal of Chemical amp Engineering Data vol53 no 7 pp 1424ndash1430 2008

[59] S Kumar and B V Babu ldquoProcess intensification of nicotinicacid production via enzymatic conversion using reactive extrac-tionrdquo Chemical and Biochemical Engineering Quarterly vol 23no 3 pp 367ndash376 2009

[60] Z Gu B Glatz and C E Glatz ldquoPropionic acid production byextractive fermentation I Solvent considerationsrdquo Biotechnol-ogy and Bioengineering vol 57 pp 454ndash461 1998

[61] C Q Ma J C Li J H Qiu M Wang and P Xu ldquoRecoveryof pyruvic acid from biotransformation solutionsrdquo AppliedMicrobiology and Biotechnology vol 70 no 3 pp 308ndash3142006

[62] T Kirsch and G Maurer ldquoDistribution of binary mixturesof citric acetic and oxalic acid between water and organicsolutions of tri-n-octylamine Part I Organic solvent toluenerdquoFluid Phase Equilibria vol 131 no 1-2 pp 213ndash231 1997

[63] R Canari and A M Eyal ldquoSelectivity in monocarboxylic acidsextraction from their mixture solutions using an amine-basedextractant effect of pHrdquo Industrial and Engineering ChemistryResearch vol 42 no 7 pp 1301ndash1307 2003

[64] M Siebold P van Frieling R Joppien D Rindfleisch KSchugerl andHRoper ldquoComparison of the production of lacticacid by three different lactobacilli and its recovery by extractionand electrodialysisrdquo Process Biochemistry vol 30 no 1 pp 81ndash95 1995

[65] T A Barbari and C J King ldquoEquilibrium distribution coeffi-cients for extraction of chlorinated hydrocarbons and aromaticsfrom water into undecanerdquo Environmental Science and Technol-ogy vol 16 no 9 pp 624ndash627 1982

[66] C L Munson and C J King ldquoFactors influencing solventselection for extraction of ethanol from aqueous solutionsrdquoIndustrial amp Engineering Chemistry Process Design and Devel-opment vol 23 no 1 pp 109ndash115 1984


[67] P D Mackenzie and C J King ldquoCombined solvent extractionand stripping for removal and isolation of ammonia from sourwatersrdquo Industrial and Engineering Chemistry Process Designand Development vol 24 no 4 pp 1192ndash1200 1985

[68] S T Yang S A White and S T Hsu ldquoExtraction of carboxylicacids with tertiary and quaternary amines effect of pHrdquoIndustrial amp Engineering Chemistry Research vol 30 no 6 pp1335ndash1342 1991

[69] J Prochazka A Heyberger V Bızek M Kousova and EVolaufova ldquoAmine extraction of hydroxycarboxylic acids 2Comparison of equilibria for lactic malic and citric acidsrdquoIndustrial and Engineering Chemistry Research vol 33 no 6 pp1565ndash1573 1994

[70] R-S Juang R-H Huang and R-T Wu ldquoSeparation of citricand lactic acids in aqueous solutions by solvent extraction andliquid membrane processesrdquo Journal of Membrane Science vol136 no 1-2 pp 89ndash99 1997

[71] F A Poposka K Nikolovski and R Tomovska ldquoEquilibriaand mathematical models of extraction of citric acid withisodecanoln-paraffins solutions of trioctylaminerdquo Journal ofChemical Engineering of Japan vol 30 no 5 pp 777ndash785 1997

[72] MMatsumoto T Otono andK Kondo ldquoSynergistic extractionof organic acids with tri-n-octylamine and tri-n-butylphos-phaterdquo Separation and Purification Technology vol 24 no 1-2pp 337ndash342 2001

[73] D Yankov J Molinier J Albet G Malmary and G Kyu-choukov ldquoLactic acid extraction from aqueous solutions withtri-n-octylamine dissolved in decanol and dodecanerdquo Biochem-ical Engineering Journal vol 21 no 1 pp 63ndash71 2004

[74] M J Kamlet J L M Abboud M H Abraham and R W TaftldquoLinear solvation energy relationships 23 A comprehensivecollection of the solvatochromic parameters 120587lowast 120573 and 120572 andsome methods for simplifying the generalized solvatochromicequationrdquo Journal of Organic Chemistry vol 48 no 17 pp 2877ndash2887 1983

[75] M H Abraham ldquoScales of solute hydrogen-bonding their con-struction and application to physicochemical and biochemicalprocessesrdquo Chemical Society Reviews vol 22 no 2 pp 73ndash831993

[76] M H Abraham J M R Gola J E Cometto-Muniz and W SCain ldquoThe solvation properties of nitric oxiderdquo Journal of theChemical Society Perkin Transactions 2 no 10 pp 2067ndash20702000

[77] V Bızek J Horacek and M Kousova ldquoAmine extraction ofcitric acid effect of diluentrdquo Chemical Engineering Science vol48 no 8 pp 1447ndash1457 1993

[78] Y-S Jun Y S Huh H HWon and Y K Hong ldquoKinetics of theextraction of succinic acid with tri-n-octylamine in 1-octanolsolutionrdquo Biotechnology Progress vol 21 no 6 pp 1673ndash16792005

[79] L K Doraiswamy andMM SharmaHeterogeneous ReactionsAnalysis Examples and Reactor Design John Wiley amp SonsNew York NY USA 1st edition 1984

[80] Y-S Jun E Z Lee Y S Huh Y K Hong W H Hong and S YLee ldquoKinetic study for the extraction of succinic acid with TOAin fermentation broth effects of pH salt and contaminatedacidrdquo Biochemical Engineering Journal vol 36 no 1 pp 8ndash132007

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


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Applied ChemistryJournal of



Theoretical ChemistryJournal of


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Analytical ChemistryInternational Journal of


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ElectrochemistryInternational Journal of



CatalystsJournal of


(ii) the acid can be reextracted and the solvent can bereused

(iii) better control of pH in the bioreactor(iv) better recovery of acid with higher product purity(v) reduction of downstream processing load and recov-

ery cost(vi) reactants are relatively immiscible(vii) product(s) undergoes subsequent undesired reac-

tions in reaction phase(viii) reaction products to be separated are immiscible with

the reaction phase(ix) phase equilibrium can be positively influenced(x) heat transfer is to be improved during the reaction(xi) product-catalyst separation can be affected by a

liquid-liquid separation

Kertes and King [3] categorize the extractants as threemajor types

(i) carbon bonded oxygen bearing extractants(ii) phosphorus bonded oxygen bearing extractants(iii) high molecular weight aliphatic amines

The first two categories are nonreactive in nature andextract the acid molecules by solvation The distinctionbetween the first two categories is based on the strengthof the solvation bonds and the specificity of solvation Thecoordinate bonds between carbon bonded oxygen donorextractant and the acid are too weak for a specific solvationbut it is significantly more for phosphorus bonded oxygenbearing extractants The extractants in the second categorymake the solvation process more specific and the numberof solvating molecules per extracted acid molecule can beaccessible experimentally The aliphatic amines in the thirdcategory can react with the carboxylic acid molecule andform acid-amine complexes by proton transfer or by ion pairformation This causes a significant increase in the distribu-tion coefficient of the carboxylic acid [11] Among aliphaticamines primary alkyl amines are observed to be excessivelysoluble inwater at room temperature while secondary aminesform a gel phase (third phase) at the interface which createdifficulty in phase separation [3]The extractability of tertiaryamines is found to be more than that of the primary andsecondary amines [5] Aliphatic tertiary amines having morethan six carbon atoms per chain are found to be effectiveextractants for the recovery of carboxylic acids [3]

Although a tertiary amine has good extractability itmust always be used with a diluent due to its viscous andcorrosive nature Further the stability of the formed acid-amine complexes in the reactive extraction is affected by thebasicity of the amine which can be manipulated by usingdifferent types of diluents Moreover use of a diluent controlsthe physical properties such as density viscosity and surfacetension of the organic phase [12]

Diluents can be broadly divided into two groups (i)active diluents and (ii) inactive diluents Generally the active

diluents are polar in nature due to the presence of functionalgroups They are good solvating media for an ion-pairsuch as an acid-amine complex [13] The category includeschlorinated hydrocarbon ketone alcohol and halogenatedaromatic solvents Inactive diluents being nonpolar providevery low distribution of the acid and poor solvation of thepolar complexes Alkanes benzene alkyl substituted aromat-ics and so forth fall in this category These diluents limit theformation of the third phase at higher concentrations of acidin the organic phase and are useful in the stripping of acidThe equilibrium curve can be shifted towards the aqueousphase by increasing the concentration of the inert diluent inthe mixture of diluents [14]

Reactive extraction represents a reaction between the acid(solute) and extractant molecule at the interface of aqueousand organic phase where transfers of acid molecules takeplace by the diffusion and solubilizationmechanism Reactiveextraction strongly depends on various parameters suchas aqueous phase composition organic phase compositiontypes of complexes (1 1 2 1 etc) formed properties of thesolvent (extractant and diluent) type of solvent temperatureand pH [15] The purpose should be achieving a highdistribution coefficient with higher selectivity This can berealized by utilizing an appropriate organic phase at optimumconditions

There are two stages in extractive separation (Figure 1)The first is the extraction of the solute to produce a solute-extractant complex and a relatively solute free aqueousraffinateThe second step is necessary for stripping the solutefrom the organic complex to obtain amine free aqueous soluteas a product and also for simultaneously regenerating theextractant recycled back to the extraction unit In the secondstage of reactive extraction it is necessary to regenerate theorganic phase Tamada and King [16] have described twoapproaches for the regeneration of extractant-diluent system(i) temperature swing regeneration and (ii) diluent swingregeneration Yabannavar and Wang [17] have purified lacticacid from a loaded organic phase using sodium hydroxide(NaOH) and hydrochloric acid (HCl) Poole and King [18]have used an aqueous solution of lowmolecular weight aminefor complete regeneration of organic phase

Reactive extraction has many applications in chemicaland pharmaceutical industries (intermediates organic acidsvitamins ) or in hydrometallurgical and environmentalscience (heavy metals inorganic acids ) The liquid ionexchangers are used to promote a certain reaction to accom-plish very selective separations [19] There are many liquidion exchangers commercially available They work basicallywith three different types of mechanisms anion exchangecation exchange and solvation It is practical to use ion-exchangers in a diluent which is immiscible with water sincethey are highly viscous or solid materials The diluent makesthe organic phase easier to handle [1]

There are a significant number of studies on reactiveextraction of organic acids in the literature These studiesinvestigate various aspects of reactive extraction of organicacids chemical interactions between acids and extractantsreaction mechanisms type of extractants and diluents effectof temperature and pH effect of aqueous and organic phase





HCaq HCorg

Cminus

aq + H3O+











119886values They
















Table1Ex

tractantdilu

entsystem

forthe

recovery

ofcarboxylicacid

byreactiv

eextraction

equilib

rium

studies

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

1Differentcarbo

xylic

acids

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofcarboxylicacids

[3]

2Lacticacid

TOA

Hexane

Type

ofacid

andinitialacid

concentration

Hydroph

obicity

ofthea

cid

controlsequilib

rium

constants

[20]

3Ac

eticlactic

succinic

malon

icfum

aricand

maleic

Tri-a

lkylam

ine(Alamine3

36)

Methylisobu

tylketon

e(MIBK)


(DCM

)andnitro

benzene

Effectsof

diluent-c

omplex

interactions

Equilib

rium

constantspartition

coeffi

cientand

dimerization

constant

determ

ined

[13]

4Citric

Alamine3


MIBK

1-octanolD

CMand

chloroform

Effecto

fdilu

ents

119870

11

11987012

and119870

23

arec

orrelated

with

solvatochrom

icparameters

[12]

6Lactic

TOA

Xylene


Aconcentration

(11)(12)and(31)a

cid-TO

Acomplexes

form

ed[21]

7(L+)

lactic

Tri-p

ropylamine(TP

A)a

ndTO

A1-o

ctanolandheptane

Acid

andam

inec

oncentratio

nMixed

tertiary

amineo

fsho

rtandlong

chaincanfacilitatee

asy

phases

eparation

[22]

8Citriclacticand

malic

Tri-iso-octylam

ine(TIOA)

1-octanolandheptane

Effecto

fmod

ifier

andtype

ofacid

Extractio

nmechanism

isprop

osed

consideringph

ysical

andchem

icalextractio

n[23]

9Glyoxylicglycolic

acrylicand

benzoic

Tri-a

lkylph

osph

ineo

xide

(TRP

O)

Kerosene

Aqueou

sand

organicp

hase

compo

sitions

Equilib

rium

mod

elfor11987011

isprop

osed

[24]

10Prop

ionic

Aliq

uat336

Cyclo

hexanehexanetoluene

MIBK

ethylacetatehexane+

MIBK

hexane

+tolueneand

MIBK+toluene

Effecto

fdilu

entand

diluent

mixtureacidandam

ine

concentration

Order

ofextractio

nethylacetate


toluenegt

hexane

+MIBKgt

toluene+

hexanegtcyclo

hexane

gthexane

[25]

11Prop

ionic

Tri-119899

-butylph

osph

ate(TB

P)

TOAand

Aliq

uat336

1-Octanol

Acid

andextractant

concentration

Order

ofextractib

ilityisfoun

dto

beTO

AgtAliq

uat336gtTB

P11

complex

form

ed[26]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

12Ita

conicmaleicmalic

oxalictartaric

and

succinic

TBP

Do-decane

pHandinitialacid

concentration

Mechanism

ofdi-carbo

xylic

acidsisp

ropo

sed

[27]

13Nicotinic

TOPO

andTB

P


1-octanolM

IBK

diethylether

decanekerosene+

1-octanol

andheptane+

1-octanol

Effecto

fdilu

entextractant

type

initialacidand

extractant

concentration

Solvationnu

mbera

ndequilib

rium

extractio

nconstants

ared

etermined

[28]

14Levulin

ic119899-Lauryltri-

alkyl-m

ethylamine

(AmberliteLA

-2)

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanoldiisob

utylketone

(DIBK)

and

MIBK

Dilu

enteffectand

amine

concentration

LSER

mod

elprop

osed

and119870

11

119870

21

and119870

31

ared

etermined

[29]

15Fo

rmic

AmberliteLA

-2

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanolD

IBK

andMIBK

Effecto

fdilu

entand

amine

concentration

Extractio

nconstants(119870

51

11987061

and119870

71

)wered

etermined

and

LSER

mod

elprop

osed

[30]

16Nicotinic

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofnicotin

icacid

[31]

17Glycolic

AmberliteLA

-21-O

ctanolcyclohexane


ne

andMIBK

Solventtypeam

inea

ndacid

concentration

Order

ofextractio

nMIBKgt

2-octano

negt1-o

ctanolgttoluene

gtiso

-octanegt

cyclo

hexane

[32]

18Citric

Tri-d

odecylam

ine(TD

DA)a

ndAmberliteLA

-2

MIBK

1-octanoltoluene

cyclo


1-octanol+MIBK

MIBK+

toluene1-o

ctanol+toluene

1-octanol+MIBK

MIBK+

tolueneandiso

-octane

Dilu

enteffectaminea

ndacid

concentration

1-Octanolprop

osed

tobe

most

effectiv

esolvent

[33]

19Glutaric

TOA

Isoamylalcoho

l1-o

ctanol

1-non

anol1-decanolm

ethyl

ethylketon

e(MEK

)diiso

butyl

ketone

(DIBK)

hexan-2-one

toluenekeroseneand

hexane

Dilu

enteffectaminea

ndacid

concentration

Kerosene

isfoun

dto

bethem

ost

effectiv

edilu

entEq

uilib

rium

constantsfor

11and

21

complex

aree

stim

ated

[34]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

20Lactic

TBP

Dod

ecane

Acid

andsolventcom

position

change

inthep

hase

volumes

and

pH

Apparent

equilib

rium

constants

andthen

umbero

freacting

extractant

molecules

[35]

21Ac

rylic

AmberliteLA

-2Cy

clohexane2-octanon

etolueneMIBK

iso-octane

hexaneand

1-octanol

Type

ofdiluentandam

ine

concentration

11amp

12acid-aminec

omplexes

forp

roton-do

natin

gdiluentsand

11amp

23for

non-proton

-don

atingdiluents


11

119870

12

and119870

23

)

[36]

22Fo

rmic

TDDAandTB


diethylsebacate1-o

ctanoland

heptane

Effecto

fdilu

entacid

andam

ine

concentration

Com

parativ

estudy

ofph

ysical

andchem

icalextractio

nTD

DA

suggestedto

betheb

est

extractant

[37]

23PenicillinG

Di-119899

-octylam

ineTO

AN

235(a

mixture

oftertiary

amines)TB


hospho

ricacid

(D2E

HPA

)

n-Bu

tylacetateM

IBK

2-ethyl

hexano

lkeroseneand

heptane

Initialacid

concentration

pHandtemperature

Effecto

fextractanto

nthe

stabilityof

penicillinGmainly

depend

sontemperature

degradationof

penicillinGin

alkalisolutio

nisgoverned

bypH

mechanism

ofdegradation

discussed

[38]

24Succinic

AmberliteLA

-2Hexanecyclo

hexanetoluene

iso-octaneMIBK

2-octano

ne

and1-o

ctanol

Initialextractant

concentration

Extractio

nconstants(1112amp

23)

foun

dou

tordero

fextractio

nof

diluents

1-octanol

gt2-octano

negtMIBKgttoluene

gtiso

-octanegt

hexanegt

cyclo

hexane

[39]

25Ita

conic

TBPandAliq

uat336

Sunfl

ower

oil

Initialacid

andextractant

concentration

Non

toxics

ystem

prop

osed

[40]

26Prop

ionic

TBP

Kerosene

and1-d

ecanol

Aqueou

sand

organicp

hase

compo

sitionsand

temperature

Mod

ifier

hasa

stron

geffecto

ndegree

ofextractio

n[41]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

27L(+)T

artaric

AmberliteLA

-21-o

ctanolcyclohexane


Organicph

asec

ompo

sitions

Extractabilityof

acid

ishigh

especiallywith

polarsolvents

(MIBKand1-o

ctanol)

[42]

28Ca

proic

TBP

MIBKandxylene

Phasec

ompo

sitions

MIBKisab

ettersolvent

than

xylene

[43]

29Ac

etic

TOA

DCM


and1-o

ctanol

Organicph

asec

ompo

sitions

and

pH

Thes

olvent

polaritycontrolsthe

form

edstr

ucture

ofthe

interfa

cialacid

andTO

Acompo

unds

[44]

30Picolin

icTB

PSunfl

ower

andcasto

roil

Aqueou

sand

organicp

hase

compo

sitions

Differentm

odels

areu

sedto

representthe

equilib

rium

data

[45]

31Picolin

icTrialkylam

ine(N235)T

BPTetrachlorom

ethanekerosene

and1-o

ctanol

Aqueou

sand

organicp

hase

compo

sitionsand

pH

Distrib

utioncoeffi

cienth

ighly

depend

ento

npH

andthe

apparent

alkalin

ityof

N2351-o

ctanol

[46]

32Ac

eticpropion

ic

butyric

andvaleric

TBP

Cyclo

hexanesulfonated

keroseneand

1-octanol

Equilib

rium

timetemperature

andph

aser

atio

Con

ditio

nsof

extractio

nand

strip

ping

arefou

nd[47]

33Citric

TOA

Rice

bran

oilsunfl

ower

oil


ilAq

ueou

sand

organica

ndph

ase

compo

sitions

Overallextractio

nconstantsa

ndassociationnu

mbers

[48]








119870

119886=

[H+] [Cminus][HC]

(2)


119862HC = [HC] + [Cminus] (3)

[HC] =119862HC

(1 + (119870

119886 [H+]))

(4)


HClarrrarr HC (5)

119875 =

[HC][HC]

(6)


2HClarrrarr (HC)2

(7)


119863 =

(HC)2

(HC)2

(8)


119863

119870

diluent119863

=

119862

diluentHC

119862

diluentHC

(9)



diluentHC is



diluent119863


119870

diluent119863

= 119875 + 2119863119875

2

[HC] (10)


119863











119864) as

given by (14)

119898HC + 119899Slarrrarr (HC)119898(119878)

119899

(13)

119870

119864=

[(HC)119898(119878)

119899

]

[HC]119898 [S]119899 (14)


119870

119863=

119862HC119862HC

= 119898

[(HC)119898(119878)

119899

]

119862HC

(15)


119899


119870

119864=

119870

119863(1 + 119870

119886 [H+])119898

119898119862

119898minus1

HC [S]119899

(16)


[S] = [S]in minus 119899 [(HC)119898(S)119899

] (17)

[S] = [S]inminus

119870

119863119899119862HC119898

(18)



119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)



119863





3(S) (22)


(23)


and119870


119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C



119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)


11

119870

21 11987031


11

C21 C31 and C




119885 =

119862HC

[S]in

(30)


11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)


119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)


) as

119870

chem119863

=


119862HC

(33)


119863


119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





HCaq HCorg

Cminus

aq + H3O+











119886values They
















Table1Ex

tractantdilu

entsystem

forthe

recovery

ofcarboxylicacid

byreactiv

eextraction

equilib

rium

studies

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

1Differentcarbo

xylic

acids

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofcarboxylicacids

[3]

2Lacticacid

TOA

Hexane

Type

ofacid

andinitialacid

concentration

Hydroph

obicity

ofthea

cid

controlsequilib

rium

constants

[20]

3Ac

eticlactic

succinic

malon

icfum

aricand

maleic

Tri-a

lkylam

ine(Alamine3

36)

Methylisobu

tylketon

e(MIBK)


(DCM

)andnitro

benzene

Effectsof

diluent-c

omplex

interactions

Equilib

rium

constantspartition

coeffi

cientand

dimerization

constant

determ

ined

[13]

4Citric

Alamine3


MIBK

1-octanolD

CMand

chloroform

Effecto

fdilu

ents

119870

11

11987012

and119870

23

arec

orrelated

with

solvatochrom

icparameters

[12]

6Lactic

TOA

Xylene


Aconcentration

(11)(12)and(31)a

cid-TO

Acomplexes

form

ed[21]

7(L+)

lactic

Tri-p

ropylamine(TP

A)a

ndTO

A1-o

ctanolandheptane

Acid

andam

inec

oncentratio

nMixed

tertiary

amineo

fsho

rtandlong

chaincanfacilitatee

asy

phases

eparation

[22]

8Citriclacticand

malic

Tri-iso-octylam

ine(TIOA)

1-octanolandheptane

Effecto

fmod

ifier

andtype

ofacid

Extractio

nmechanism

isprop

osed

consideringph

ysical

andchem

icalextractio

n[23]

9Glyoxylicglycolic

acrylicand

benzoic

Tri-a

lkylph

osph

ineo

xide

(TRP

O)

Kerosene

Aqueou

sand

organicp

hase

compo

sitions

Equilib

rium

mod

elfor11987011

isprop

osed

[24]

10Prop

ionic

Aliq

uat336

Cyclo

hexanehexanetoluene

MIBK

ethylacetatehexane+

MIBK

hexane

+tolueneand

MIBK+toluene

Effecto

fdilu

entand

diluent

mixtureacidandam

ine

concentration

Order

ofextractio

nethylacetate


toluenegt

hexane

+MIBKgt

toluene+

hexanegtcyclo

hexane

gthexane

[25]

11Prop

ionic

Tri-119899

-butylph

osph

ate(TB

P)

TOAand

Aliq

uat336

1-Octanol

Acid

andextractant

concentration

Order

ofextractib

ilityisfoun

dto

beTO

AgtAliq

uat336gtTB

P11

complex

form

ed[26]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

12Ita

conicmaleicmalic

oxalictartaric

and

succinic

TBP

Do-decane

pHandinitialacid

concentration

Mechanism

ofdi-carbo

xylic

acidsisp

ropo

sed

[27]

13Nicotinic

TOPO

andTB

P


1-octanolM

IBK

diethylether

decanekerosene+

1-octanol

andheptane+

1-octanol

Effecto

fdilu

entextractant

type

initialacidand

extractant

concentration

Solvationnu

mbera

ndequilib

rium

extractio

nconstants

ared

etermined

[28]

14Levulin

ic119899-Lauryltri-

alkyl-m

ethylamine

(AmberliteLA

-2)

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanoldiisob

utylketone

(DIBK)

and

MIBK

Dilu

enteffectand

amine

concentration

LSER

mod

elprop

osed

and119870

11

119870

21

and119870

31

ared

etermined

[29]

15Fo

rmic

AmberliteLA

-2

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanolD

IBK

andMIBK

Effecto

fdilu

entand

amine

concentration

Extractio

nconstants(119870

51

11987061

and119870

71

)wered

etermined

and

LSER

mod

elprop

osed

[30]

16Nicotinic

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofnicotin

icacid

[31]

17Glycolic

AmberliteLA

-21-O

ctanolcyclohexane


ne

andMIBK

Solventtypeam

inea

ndacid

concentration

Order

ofextractio

nMIBKgt

2-octano

negt1-o

ctanolgttoluene

gtiso

-octanegt

cyclo

hexane

[32]

18Citric

Tri-d

odecylam

ine(TD

DA)a

ndAmberliteLA

-2

MIBK

1-octanoltoluene

cyclo


1-octanol+MIBK

MIBK+

toluene1-o

ctanol+toluene

1-octanol+MIBK

MIBK+

tolueneandiso

-octane

Dilu

enteffectaminea

ndacid

concentration

1-Octanolprop

osed

tobe

most

effectiv

esolvent

[33]

19Glutaric

TOA

Isoamylalcoho

l1-o

ctanol

1-non

anol1-decanolm

ethyl

ethylketon

e(MEK

)diiso

butyl

ketone

(DIBK)

hexan-2-one

toluenekeroseneand

hexane

Dilu

enteffectaminea

ndacid

concentration

Kerosene

isfoun

dto

bethem

ost

effectiv

edilu

entEq

uilib

rium

constantsfor

11and

21

complex

aree

stim

ated

[34]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

20Lactic

TBP

Dod

ecane

Acid

andsolventcom

position

change

inthep

hase

volumes

and

pH

Apparent

equilib

rium

constants

andthen

umbero

freacting

extractant

molecules

[35]

21Ac

rylic

AmberliteLA

-2Cy

clohexane2-octanon

etolueneMIBK

iso-octane

hexaneand

1-octanol

Type

ofdiluentandam

ine

concentration

11amp

12acid-aminec

omplexes

forp

roton-do

natin

gdiluentsand

11amp

23for

non-proton

-don

atingdiluents


11

119870

12

and119870

23

)

[36]

22Fo

rmic

TDDAandTB


diethylsebacate1-o

ctanoland

heptane

Effecto

fdilu

entacid

andam

ine

concentration

Com

parativ

estudy

ofph

ysical

andchem

icalextractio

nTD

DA

suggestedto

betheb

est

extractant

[37]

23PenicillinG

Di-119899

-octylam

ineTO

AN

235(a

mixture

oftertiary

amines)TB


hospho

ricacid

(D2E

HPA

)

n-Bu

tylacetateM

IBK

2-ethyl

hexano

lkeroseneand

heptane

Initialacid

concentration

pHandtemperature

Effecto

fextractanto

nthe

stabilityof

penicillinGmainly

depend

sontemperature

degradationof

penicillinGin

alkalisolutio

nisgoverned

bypH

mechanism

ofdegradation

discussed

[38]

24Succinic

AmberliteLA

-2Hexanecyclo

hexanetoluene

iso-octaneMIBK

2-octano

ne

and1-o

ctanol

Initialextractant

concentration

Extractio

nconstants(1112amp

23)

foun

dou

tordero

fextractio

nof

diluents

1-octanol

gt2-octano

negtMIBKgttoluene

gtiso

-octanegt

hexanegt

cyclo

hexane

[39]

25Ita

conic

TBPandAliq

uat336

Sunfl

ower

oil

Initialacid

andextractant

concentration

Non

toxics

ystem

prop

osed

[40]

26Prop

ionic

TBP

Kerosene

and1-d

ecanol

Aqueou

sand

organicp

hase

compo

sitionsand

temperature

Mod

ifier

hasa

stron

geffecto

ndegree

ofextractio

n[41]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

27L(+)T

artaric

AmberliteLA

-21-o

ctanolcyclohexane


Organicph

asec

ompo

sitions

Extractabilityof

acid

ishigh

especiallywith

polarsolvents

(MIBKand1-o

ctanol)

[42]

28Ca

proic

TBP

MIBKandxylene

Phasec

ompo

sitions

MIBKisab

ettersolvent

than

xylene

[43]

29Ac

etic

TOA

DCM


and1-o

ctanol

Organicph

asec

ompo

sitions

and

pH

Thes

olvent

polaritycontrolsthe

form

edstr

ucture

ofthe

interfa

cialacid

andTO

Acompo

unds

[44]

30Picolin

icTB

PSunfl

ower

andcasto

roil

Aqueou

sand

organicp

hase

compo

sitions

Differentm

odels

areu

sedto

representthe

equilib

rium

data

[45]

31Picolin

icTrialkylam

ine(N235)T

BPTetrachlorom

ethanekerosene

and1-o

ctanol

Aqueou

sand

organicp

hase

compo

sitionsand

pH

Distrib

utioncoeffi

cienth

ighly

depend

ento

npH

andthe

apparent

alkalin

ityof

N2351-o

ctanol

[46]

32Ac

eticpropion

ic

butyric

andvaleric

TBP

Cyclo

hexanesulfonated

keroseneand

1-octanol

Equilib

rium

timetemperature

andph

aser

atio

Con

ditio

nsof

extractio

nand

strip

ping

arefou

nd[47]

33Citric

TOA

Rice

bran

oilsunfl

ower

oil


ilAq

ueou

sand

organica

ndph

ase

compo

sitions

Overallextractio

nconstantsa

ndassociationnu

mbers

[48]








119870

119886=

[H+] [Cminus][HC]

(2)


119862HC = [HC] + [Cminus] (3)

[HC] =119862HC

(1 + (119870

119886 [H+]))

(4)


HClarrrarr HC (5)

119875 =

[HC][HC]

(6)


2HClarrrarr (HC)2

(7)


119863 =

(HC)2

(HC)2

(8)


119863

119870

diluent119863

=

119862

diluentHC

119862

diluentHC

(9)



diluentHC is



diluent119863


119870

diluent119863

= 119875 + 2119863119875

2

[HC] (10)


119863











119864) as

given by (14)

119898HC + 119899Slarrrarr (HC)119898(119878)

119899

(13)

119870

119864=

[(HC)119898(119878)

119899

]

[HC]119898 [S]119899 (14)


119870

119863=

119862HC119862HC

= 119898

[(HC)119898(119878)

119899

]

119862HC

(15)


119899


119870

119864=

119870

119863(1 + 119870

119886 [H+])119898

119898119862

119898minus1

HC [S]119899

(16)


[S] = [S]in minus 119899 [(HC)119898(S)119899

] (17)

[S] = [S]inminus

119870

119863119899119862HC119898

(18)



119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)



119863





3(S) (22)


(23)


and119870


119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C



119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)


11

119870

21 11987031


11

C21 C31 and C




119885 =

119862HC

[S]in

(30)


11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)


119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)


) as

119870

chem119863

=


119862HC

(33)


119863


119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of












Table1Ex

tractantdilu

entsystem

forthe

recovery

ofcarboxylicacid

byreactiv

eextraction

equilib

rium

studies

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

1Differentcarbo

xylic

acids

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofcarboxylicacids

[3]

2Lacticacid

TOA

Hexane

Type

ofacid

andinitialacid

concentration

Hydroph

obicity

ofthea

cid

controlsequilib

rium

constants

[20]

3Ac

eticlactic

succinic

malon

icfum

aricand

maleic

Tri-a

lkylam

ine(Alamine3

36)

Methylisobu

tylketon

e(MIBK)


(DCM

)andnitro

benzene

Effectsof

diluent-c

omplex

interactions

Equilib

rium

constantspartition

coeffi

cientand

dimerization

constant

determ

ined

[13]

4Citric

Alamine3


MIBK

1-octanolD

CMand

chloroform

Effecto

fdilu

ents

119870

11

11987012

and119870

23

arec

orrelated

with

solvatochrom

icparameters

[12]

6Lactic

TOA

Xylene


Aconcentration

(11)(12)and(31)a

cid-TO

Acomplexes

form

ed[21]

7(L+)

lactic

Tri-p

ropylamine(TP

A)a

ndTO

A1-o

ctanolandheptane

Acid

andam

inec

oncentratio

nMixed

tertiary

amineo

fsho

rtandlong

chaincanfacilitatee

asy

phases

eparation

[22]

8Citriclacticand

malic

Tri-iso-octylam

ine(TIOA)

1-octanolandheptane

Effecto

fmod

ifier

andtype

ofacid

Extractio

nmechanism

isprop

osed

consideringph

ysical

andchem

icalextractio

n[23]

9Glyoxylicglycolic

acrylicand

benzoic

Tri-a

lkylph

osph

ineo

xide

(TRP

O)

Kerosene

Aqueou

sand

organicp

hase

compo

sitions

Equilib

rium

mod

elfor11987011

isprop

osed

[24]

10Prop

ionic

Aliq

uat336

Cyclo

hexanehexanetoluene

MIBK

ethylacetatehexane+

MIBK

hexane

+tolueneand

MIBK+toluene

Effecto

fdilu

entand

diluent

mixtureacidandam

ine

concentration

Order

ofextractio

nethylacetate


toluenegt

hexane

+MIBKgt

toluene+

hexanegtcyclo

hexane

gthexane

[25]

11Prop

ionic

Tri-119899

-butylph

osph

ate(TB

P)

TOAand

Aliq

uat336

1-Octanol

Acid

andextractant

concentration

Order

ofextractib

ilityisfoun

dto

beTO

AgtAliq

uat336gtTB

P11

complex

form

ed[26]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

12Ita

conicmaleicmalic

oxalictartaric

and

succinic

TBP

Do-decane

pHandinitialacid

concentration

Mechanism

ofdi-carbo

xylic

acidsisp

ropo

sed

[27]

13Nicotinic

TOPO

andTB

P


1-octanolM

IBK

diethylether

decanekerosene+

1-octanol

andheptane+

1-octanol

Effecto

fdilu

entextractant

type

initialacidand

extractant

concentration

Solvationnu

mbera

ndequilib

rium

extractio

nconstants

ared

etermined

[28]

14Levulin

ic119899-Lauryltri-

alkyl-m

ethylamine

(AmberliteLA

-2)

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanoldiisob

utylketone

(DIBK)

and

MIBK

Dilu

enteffectand

amine

concentration

LSER

mod

elprop

osed

and119870

11

119870

21

and119870

31

ared

etermined

[29]

15Fo

rmic

AmberliteLA

-2

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanolD

IBK

andMIBK

Effecto

fdilu

entand

amine

concentration

Extractio

nconstants(119870

51

11987061

and119870

71

)wered

etermined

and

LSER

mod

elprop

osed

[30]

16Nicotinic

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofnicotin

icacid

[31]

17Glycolic

AmberliteLA

-21-O

ctanolcyclohexane


ne

andMIBK

Solventtypeam

inea

ndacid

concentration

Order

ofextractio

nMIBKgt

2-octano

negt1-o

ctanolgttoluene

gtiso

-octanegt

cyclo

hexane

[32]

18Citric

Tri-d

odecylam

ine(TD

DA)a

ndAmberliteLA

-2

MIBK

1-octanoltoluene

cyclo


1-octanol+MIBK

MIBK+

toluene1-o

ctanol+toluene

1-octanol+MIBK

MIBK+

tolueneandiso

-octane

Dilu

enteffectaminea

ndacid

concentration

1-Octanolprop

osed

tobe

most

effectiv

esolvent

[33]

19Glutaric

TOA

Isoamylalcoho

l1-o

ctanol

1-non

anol1-decanolm

ethyl

ethylketon

e(MEK

)diiso

butyl

ketone

(DIBK)

hexan-2-one

toluenekeroseneand

hexane

Dilu

enteffectaminea

ndacid

concentration

Kerosene

isfoun

dto

bethem

ost

effectiv

edilu

entEq

uilib

rium

constantsfor

11and

21

complex

aree

stim

ated

[34]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

20Lactic

TBP

Dod

ecane

Acid

andsolventcom

position

change

inthep

hase

volumes

and

pH

Apparent

equilib

rium

constants

andthen

umbero

freacting

extractant

molecules

[35]

21Ac

rylic

AmberliteLA

-2Cy

clohexane2-octanon

etolueneMIBK

iso-octane

hexaneand

1-octanol

Type

ofdiluentandam

ine

concentration

11amp

12acid-aminec

omplexes

forp

roton-do

natin

gdiluentsand

11amp

23for

non-proton

-don

atingdiluents


11

119870

12

and119870

23

)

[36]

22Fo

rmic

TDDAandTB


diethylsebacate1-o

ctanoland

heptane

Effecto

fdilu

entacid

andam

ine

concentration

Com

parativ

estudy

ofph

ysical

andchem

icalextractio

nTD

DA

suggestedto

betheb

est

extractant

[37]

23PenicillinG

Di-119899

-octylam

ineTO

AN

235(a

mixture

oftertiary

amines)TB


hospho

ricacid

(D2E

HPA

)

n-Bu

tylacetateM

IBK

2-ethyl

hexano

lkeroseneand

heptane

Initialacid

concentration

pHandtemperature

Effecto

fextractanto

nthe

stabilityof

penicillinGmainly

depend

sontemperature

degradationof

penicillinGin

alkalisolutio

nisgoverned

bypH

mechanism

ofdegradation

discussed

[38]

24Succinic

AmberliteLA

-2Hexanecyclo

hexanetoluene

iso-octaneMIBK

2-octano

ne

and1-o

ctanol

Initialextractant

concentration

Extractio

nconstants(1112amp

23)

foun

dou

tordero

fextractio

nof

diluents

1-octanol

gt2-octano

negtMIBKgttoluene

gtiso

-octanegt

hexanegt

cyclo

hexane

[39]

25Ita

conic

TBPandAliq

uat336

Sunfl

ower

oil

Initialacid

andextractant

concentration

Non

toxics

ystem

prop

osed

[40]

26Prop

ionic

TBP

Kerosene

and1-d

ecanol

Aqueou

sand

organicp

hase

compo

sitionsand

temperature

Mod

ifier

hasa

stron

geffecto

ndegree

ofextractio

n[41]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

27L(+)T

artaric

AmberliteLA

-21-o

ctanolcyclohexane


Organicph

asec

ompo

sitions

Extractabilityof

acid

ishigh

especiallywith

polarsolvents

(MIBKand1-o

ctanol)

[42]

28Ca

proic

TBP

MIBKandxylene

Phasec

ompo

sitions

MIBKisab

ettersolvent

than

xylene

[43]

29Ac

etic

TOA

DCM


and1-o

ctanol

Organicph

asec

ompo

sitions

and

pH

Thes

olvent

polaritycontrolsthe

form

edstr

ucture

ofthe

interfa

cialacid

andTO

Acompo

unds

[44]

30Picolin

icTB

PSunfl

ower

andcasto

roil

Aqueou

sand

organicp

hase

compo

sitions

Differentm

odels

areu

sedto

representthe

equilib

rium

data

[45]

31Picolin

icTrialkylam

ine(N235)T

BPTetrachlorom

ethanekerosene

and1-o

ctanol

Aqueou

sand

organicp

hase

compo

sitionsand

pH

Distrib

utioncoeffi

cienth

ighly

depend

ento

npH

andthe

apparent

alkalin

ityof

N2351-o

ctanol

[46]

32Ac

eticpropion

ic

butyric

andvaleric

TBP

Cyclo

hexanesulfonated

keroseneand

1-octanol

Equilib

rium

timetemperature

andph

aser

atio

Con

ditio

nsof

extractio

nand

strip

ping

arefou

nd[47]

33Citric

TOA

Rice

bran

oilsunfl

ower

oil


ilAq

ueou

sand

organica

ndph

ase

compo

sitions

Overallextractio

nconstantsa

ndassociationnu

mbers

[48]








119870

119886=

[H+] [Cminus][HC]

(2)


119862HC = [HC] + [Cminus] (3)

[HC] =119862HC

(1 + (119870

119886 [H+]))

(4)


HClarrrarr HC (5)

119875 =

[HC][HC]

(6)


2HClarrrarr (HC)2

(7)


119863 =

(HC)2

(HC)2

(8)


119863

119870

diluent119863

=

119862

diluentHC

119862

diluentHC

(9)



diluentHC is



diluent119863


119870

diluent119863

= 119875 + 2119863119875

2

[HC] (10)


119863











119864) as

given by (14)

119898HC + 119899Slarrrarr (HC)119898(119878)

119899

(13)

119870

119864=

[(HC)119898(119878)

119899

]

[HC]119898 [S]119899 (14)


119870

119863=

119862HC119862HC

= 119898

[(HC)119898(119878)

119899

]

119862HC

(15)


119899


119870

119864=

119870

119863(1 + 119870

119886 [H+])119898

119898119862

119898minus1

HC [S]119899

(16)


[S] = [S]in minus 119899 [(HC)119898(S)119899

] (17)

[S] = [S]inminus

119870

119863119899119862HC119898

(18)



119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)



119863





3(S) (22)


(23)


and119870


119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C



119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)


11

119870

21 11987031


11

C21 C31 and C




119885 =

119862HC

[S]in

(30)


11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)


119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)


) as

119870

chem119863

=


119862HC

(33)


119863


119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

12Ita

conicmaleicmalic

oxalictartaric

and

succinic

TBP

Do-decane

pHandinitialacid

concentration

Mechanism

ofdi-carbo

xylic

acidsisp

ropo

sed

[27]

13Nicotinic

TOPO

andTB

P


1-octanolM

IBK

diethylether

decanekerosene+

1-octanol

andheptane+

1-octanol

Effecto

fdilu

entextractant

type

initialacidand

extractant

concentration

Solvationnu

mbera

ndequilib

rium

extractio

nconstants

ared

etermined

[28]

14Levulin

ic119899-Lauryltri-

alkyl-m

ethylamine

(AmberliteLA

-2)

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanoldiisob

utylketone

(DIBK)

and

MIBK

Dilu

enteffectand

amine

concentration

LSER

mod

elprop

osed

and119870

11

119870

21

and119870

31

ared

etermined

[29]

15Fo

rmic

AmberliteLA

-2

Dim

ethylphthalatedim

ethyl



carbon

ateiso

amylalcoho

l1-h


anol

1-decanolD

IBK

andMIBK

Effecto

fdilu

entand

amine

concentration

Extractio

nconstants(119870

51

11987061

and119870

71

)wered

etermined

and

LSER

mod

elprop

osed

[30]

16Nicotinic

Organop

hospho

rous

and

aliphatic

amines

Alcoh

olsketonesethersand

hydrocarbo

nsVa

rious

aqueou

sand

organic

phasep

aram

eters

Review

edthee

xtraction

chem

istry

ofnicotin

icacid

[31]

17Glycolic

AmberliteLA

-21-O

ctanolcyclohexane


ne

andMIBK

Solventtypeam

inea

ndacid

concentration

Order

ofextractio

nMIBKgt

2-octano

negt1-o

ctanolgttoluene

gtiso

-octanegt

cyclo

hexane

[32]

18Citric

Tri-d

odecylam

ine(TD

DA)a

ndAmberliteLA

-2

MIBK

1-octanoltoluene

cyclo


1-octanol+MIBK

MIBK+

toluene1-o

ctanol+toluene

1-octanol+MIBK

MIBK+

tolueneandiso

-octane

Dilu

enteffectaminea

ndacid

concentration

1-Octanolprop

osed

tobe

most

effectiv

esolvent

[33]

19Glutaric

TOA

Isoamylalcoho

l1-o

ctanol

1-non

anol1-decanolm

ethyl

ethylketon

e(MEK

)diiso

butyl

ketone

(DIBK)

hexan-2-one

toluenekeroseneand

hexane

Dilu

enteffectaminea

ndacid

concentration

Kerosene

isfoun

dto

bethem

ost

effectiv

edilu

entEq

uilib

rium

constantsfor

11and

21

complex

aree

stim

ated

[34]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

20Lactic

TBP

Dod

ecane

Acid

andsolventcom

position

change

inthep

hase

volumes

and

pH

Apparent

equilib

rium

constants

andthen

umbero

freacting

extractant

molecules

[35]

21Ac

rylic

AmberliteLA

-2Cy

clohexane2-octanon

etolueneMIBK

iso-octane

hexaneand

1-octanol

Type

ofdiluentandam

ine

concentration

11amp

12acid-aminec

omplexes

forp

roton-do

natin

gdiluentsand

11amp

23for

non-proton

-don

atingdiluents


11

119870

12

and119870

23

)

[36]

22Fo

rmic

TDDAandTB


diethylsebacate1-o

ctanoland

heptane

Effecto

fdilu

entacid

andam

ine

concentration

Com

parativ

estudy

ofph

ysical

andchem

icalextractio

nTD

DA

suggestedto

betheb

est

extractant

[37]

23PenicillinG

Di-119899

-octylam

ineTO

AN

235(a

mixture

oftertiary

amines)TB


hospho

ricacid

(D2E

HPA

)

n-Bu

tylacetateM

IBK

2-ethyl

hexano

lkeroseneand

heptane

Initialacid

concentration

pHandtemperature

Effecto

fextractanto

nthe

stabilityof

penicillinGmainly

depend

sontemperature

degradationof

penicillinGin

alkalisolutio

nisgoverned

bypH

mechanism

ofdegradation

discussed

[38]

24Succinic

AmberliteLA

-2Hexanecyclo

hexanetoluene

iso-octaneMIBK

2-octano

ne

and1-o

ctanol

Initialextractant

concentration

Extractio

nconstants(1112amp

23)

foun

dou

tordero

fextractio

nof

diluents

1-octanol

gt2-octano

negtMIBKgttoluene

gtiso

-octanegt

hexanegt

cyclo

hexane

[39]

25Ita

conic

TBPandAliq

uat336

Sunfl

ower

oil

Initialacid

andextractant

concentration

Non

toxics

ystem

prop

osed

[40]

26Prop

ionic

TBP

Kerosene

and1-d

ecanol

Aqueou

sand

organicp

hase

compo

sitionsand

temperature

Mod

ifier

hasa

stron

geffecto

ndegree

ofextractio

n[41]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

27L(+)T

artaric

AmberliteLA

-21-o

ctanolcyclohexane


Organicph

asec

ompo

sitions

Extractabilityof

acid

ishigh

especiallywith

polarsolvents

(MIBKand1-o

ctanol)

[42]

28Ca

proic

TBP

MIBKandxylene

Phasec

ompo

sitions

MIBKisab

ettersolvent

than

xylene

[43]

29Ac

etic

TOA

DCM


and1-o

ctanol

Organicph

asec

ompo

sitions

and

pH

Thes

olvent

polaritycontrolsthe

form

edstr

ucture

ofthe

interfa

cialacid

andTO

Acompo

unds

[44]

30Picolin

icTB

PSunfl

ower

andcasto

roil

Aqueou

sand

organicp

hase

compo

sitions

Differentm

odels

areu

sedto

representthe

equilib

rium

data

[45]

31Picolin

icTrialkylam

ine(N235)T

BPTetrachlorom

ethanekerosene

and1-o

ctanol

Aqueou

sand

organicp

hase

compo

sitionsand

pH

Distrib

utioncoeffi

cienth

ighly

depend

ento

npH

andthe

apparent

alkalin

ityof

N2351-o

ctanol

[46]

32Ac

eticpropion

ic

butyric

andvaleric

TBP

Cyclo

hexanesulfonated

keroseneand

1-octanol

Equilib

rium

timetemperature

andph

aser

atio

Con

ditio

nsof

extractio

nand

strip

ping

arefou

nd[47]

33Citric

TOA

Rice

bran

oilsunfl

ower

oil


ilAq

ueou

sand

organica

ndph

ase

compo

sitions

Overallextractio

nconstantsa

ndassociationnu

mbers

[48]








119870

119886=

[H+] [Cminus][HC]

(2)


119862HC = [HC] + [Cminus] (3)

[HC] =119862HC

(1 + (119870

119886 [H+]))

(4)


HClarrrarr HC (5)

119875 =

[HC][HC]

(6)


2HClarrrarr (HC)2

(7)


119863 =

(HC)2

(HC)2

(8)


119863

119870

diluent119863

=

119862

diluentHC

119862

diluentHC

(9)



diluentHC is



diluent119863


119870

diluent119863

= 119875 + 2119863119875

2

[HC] (10)


119863











119864) as

given by (14)

119898HC + 119899Slarrrarr (HC)119898(119878)

119899

(13)

119870

119864=

[(HC)119898(119878)

119899

]

[HC]119898 [S]119899 (14)


119870

119863=

119862HC119862HC

= 119898

[(HC)119898(119878)

119899

]

119862HC

(15)


119899


119870

119864=

119870

119863(1 + 119870

119886 [H+])119898

119898119862

119898minus1

HC [S]119899

(16)


[S] = [S]in minus 119899 [(HC)119898(S)119899

] (17)

[S] = [S]inminus

119870

119863119899119862HC119898

(18)



119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)



119863





3(S) (22)


(23)


and119870


119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C



119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)


11

119870

21 11987031


11

C21 C31 and C




119885 =

119862HC

[S]in

(30)


11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)


119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)


) as

119870

chem119863

=


119862HC

(33)


119863


119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

20Lactic

TBP

Dod

ecane

Acid

andsolventcom

position

change

inthep

hase

volumes

and

pH

Apparent

equilib

rium

constants

andthen

umbero

freacting

extractant

molecules

[35]

21Ac

rylic

AmberliteLA

-2Cy

clohexane2-octanon

etolueneMIBK

iso-octane

hexaneand

1-octanol

Type

ofdiluentandam

ine

concentration

11amp

12acid-aminec

omplexes

forp

roton-do

natin

gdiluentsand

11amp

23for

non-proton

-don

atingdiluents


11

119870

12

and119870

23

)

[36]

22Fo

rmic

TDDAandTB


diethylsebacate1-o

ctanoland

heptane

Effecto

fdilu

entacid

andam

ine

concentration

Com

parativ

estudy

ofph

ysical

andchem

icalextractio

nTD

DA

suggestedto

betheb

est

extractant

[37]

23PenicillinG

Di-119899

-octylam

ineTO

AN

235(a

mixture

oftertiary

amines)TB


hospho

ricacid

(D2E

HPA

)

n-Bu

tylacetateM

IBK

2-ethyl

hexano

lkeroseneand

heptane

Initialacid

concentration

pHandtemperature

Effecto

fextractanto

nthe

stabilityof

penicillinGmainly

depend

sontemperature

degradationof

penicillinGin

alkalisolutio

nisgoverned

bypH

mechanism

ofdegradation

discussed

[38]

24Succinic

AmberliteLA

-2Hexanecyclo

hexanetoluene

iso-octaneMIBK

2-octano

ne

and1-o

ctanol

Initialextractant

concentration

Extractio

nconstants(1112amp

23)

foun

dou

tordero

fextractio

nof

diluents

1-octanol

gt2-octano

negtMIBKgttoluene

gtiso

-octanegt

hexanegt

cyclo

hexane

[39]

25Ita

conic

TBPandAliq

uat336

Sunfl

ower

oil

Initialacid

andextractant

concentration

Non

toxics

ystem

prop

osed

[40]

26Prop

ionic

TBP

Kerosene

and1-d

ecanol

Aqueou

sand

organicp

hase

compo

sitionsand

temperature

Mod

ifier

hasa

stron

geffecto

ndegree

ofextractio

n[41]


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

27L(+)T

artaric

AmberliteLA

-21-o

ctanolcyclohexane


Organicph

asec

ompo

sitions

Extractabilityof

acid

ishigh

especiallywith

polarsolvents

(MIBKand1-o

ctanol)

[42]

28Ca

proic

TBP

MIBKandxylene

Phasec

ompo

sitions

MIBKisab

ettersolvent

than

xylene

[43]

29Ac

etic

TOA

DCM


and1-o

ctanol

Organicph

asec

ompo

sitions

and

pH

Thes

olvent

polaritycontrolsthe

form

edstr

ucture

ofthe

interfa

cialacid

andTO

Acompo

unds

[44]

30Picolin

icTB

PSunfl

ower

andcasto

roil

Aqueou

sand

organicp

hase

compo

sitions

Differentm

odels

areu

sedto

representthe

equilib

rium

data

[45]

31Picolin

icTrialkylam

ine(N235)T

BPTetrachlorom

ethanekerosene

and1-o

ctanol

Aqueou

sand

organicp

hase

compo

sitionsand

pH

Distrib

utioncoeffi

cienth

ighly

depend

ento

npH

andthe

apparent

alkalin

ityof

N2351-o

ctanol

[46]

32Ac

eticpropion

ic

butyric

andvaleric

TBP

Cyclo

hexanesulfonated

keroseneand

1-octanol

Equilib

rium

timetemperature

andph

aser

atio

Con

ditio

nsof

extractio

nand

strip

ping

arefou

nd[47]

33Citric

TOA

Rice

bran

oilsunfl

ower

oil


ilAq

ueou

sand

organica

ndph

ase

compo

sitions

Overallextractio

nconstantsa

ndassociationnu

mbers

[48]








119870

119886=

[H+] [Cminus][HC]

(2)


119862HC = [HC] + [Cminus] (3)

[HC] =119862HC

(1 + (119870

119886 [H+]))

(4)


HClarrrarr HC (5)

119875 =

[HC][HC]

(6)


2HClarrrarr (HC)2

(7)


119863 =

(HC)2

(HC)2

(8)


119863

119870

diluent119863

=

119862

diluentHC

119862

diluentHC

(9)



diluentHC is



diluent119863


119870

diluent119863

= 119875 + 2119863119875

2

[HC] (10)


119863











119864) as

given by (14)

119898HC + 119899Slarrrarr (HC)119898(119878)

119899

(13)

119870

119864=

[(HC)119898(119878)

119899

]

[HC]119898 [S]119899 (14)


119870

119863=

119862HC119862HC

= 119898

[(HC)119898(119878)

119899

]

119862HC

(15)


119899


119870

119864=

119870

119863(1 + 119870

119886 [H+])119898

119898119862

119898minus1

HC [S]119899

(16)


[S] = [S]in minus 119899 [(HC)119898(S)119899

] (17)

[S] = [S]inminus

119870

119863119899119862HC119898

(18)



119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)



119863





3(S) (22)


(23)


and119870


119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C



119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)


11

119870

21 11987031


11

C21 C31 and C




119885 =

119862HC

[S]in

(30)


11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)


119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)


) as

119870

chem119863

=


119862HC

(33)


119863


119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table1Con

tinued

SL number

Carboxylicacid

Extractant

Dilu

ent

Parametersstudied

Find

ings

References

27L(+)T

artaric

AmberliteLA

-21-o

ctanolcyclohexane


Organicph

asec

ompo

sitions

Extractabilityof

acid

ishigh

especiallywith

polarsolvents

(MIBKand1-o

ctanol)

[42]

28Ca

proic

TBP

MIBKandxylene

Phasec

ompo

sitions

MIBKisab

ettersolvent

than

xylene

[43]

29Ac

etic

TOA

DCM


and1-o

ctanol

Organicph

asec

ompo

sitions

and

pH

Thes

olvent

polaritycontrolsthe

form

edstr

ucture

ofthe

interfa

cialacid

andTO

Acompo

unds

[44]

30Picolin

icTB

PSunfl

ower

andcasto

roil

Aqueou

sand

organicp

hase

compo

sitions

Differentm

odels

areu

sedto

representthe

equilib

rium

data

[45]

31Picolin

icTrialkylam

ine(N235)T

BPTetrachlorom

ethanekerosene

and1-o

ctanol

Aqueou

sand

organicp

hase

compo

sitionsand

pH

Distrib

utioncoeffi

cienth

ighly

depend

ento

npH

andthe

apparent

alkalin

ityof

N2351-o

ctanol

[46]

32Ac

eticpropion

ic

butyric

andvaleric

TBP

Cyclo

hexanesulfonated

keroseneand

1-octanol

Equilib

rium

timetemperature

andph

aser

atio

Con

ditio

nsof

extractio

nand

strip

ping

arefou

nd[47]

33Citric

TOA

Rice

bran

oilsunfl

ower

oil


ilAq

ueou

sand

organica

ndph

ase

compo

sitions

Overallextractio

nconstantsa

ndassociationnu

mbers

[48]








119870

119886=

[H+] [Cminus][HC]

(2)


119862HC = [HC] + [Cminus] (3)

[HC] =119862HC

(1 + (119870

119886 [H+]))

(4)


HClarrrarr HC (5)

119875 =

[HC][HC]

(6)


2HClarrrarr (HC)2

(7)


119863 =

(HC)2

(HC)2

(8)


119863

119870

diluent119863

=

119862

diluentHC

119862

diluentHC

(9)



diluentHC is



diluent119863


119870

diluent119863

= 119875 + 2119863119875

2

[HC] (10)


119863











119864) as

given by (14)

119898HC + 119899Slarrrarr (HC)119898(119878)

119899

(13)

119870

119864=

[(HC)119898(119878)

119899

]

[HC]119898 [S]119899 (14)


119870

119863=

119862HC119862HC

= 119898

[(HC)119898(119878)

119899

]

119862HC

(15)


119899


119870

119864=

119870

119863(1 + 119870

119886 [H+])119898

119898119862

119898minus1

HC [S]119899

(16)


[S] = [S]in minus 119899 [(HC)119898(S)119899

] (17)

[S] = [S]inminus

119870

119863119899119862HC119898

(18)



119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)



119863





3(S) (22)


(23)


and119870


119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C



119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)


11

119870

21 11987031


11

C21 C31 and C




119885 =

119862HC

[S]in

(30)


11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)


119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)


) as

119870

chem119863

=


119862HC

(33)


119863


119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of








119870

119886=

[H+] [Cminus][HC]

(2)


119862HC = [HC] + [Cminus] (3)

[HC] =119862HC

(1 + (119870

119886 [H+]))

(4)


HClarrrarr HC (5)

119875 =

[HC][HC]

(6)


2HClarrrarr (HC)2

(7)


119863 =

(HC)2

(HC)2

(8)


119863

119870

diluent119863

=

119862

diluentHC

119862

diluentHC

(9)



diluentHC is



diluent119863


119870

diluent119863

= 119875 + 2119863119875

2

[HC] (10)


119863











119864) as

given by (14)

119898HC + 119899Slarrrarr (HC)119898(119878)

119899

(13)

119870

119864=

[(HC)119898(119878)

119899

]

[HC]119898 [S]119899 (14)


119870

119863=

119862HC119862HC

= 119898

[(HC)119898(119878)

119899

]

119862HC

(15)


119899


119870

119864=

119870

119863(1 + 119870

119886 [H+])119898

119898119862

119898minus1

HC [S]119899

(16)


[S] = [S]in minus 119899 [(HC)119898(S)119899

] (17)

[S] = [S]inminus

119870

119863119899119862HC119898

(18)



119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)



119863





3(S) (22)


(23)


and119870


119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C



119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)


11

119870

21 11987031


11

C21 C31 and C




119885 =

119862HC

[S]in

(30)


11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)


119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)


) as

119870

chem119863

=


119862HC

(33)


119863


119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



119870

119863= 119898119870

119864([S]

inminus 119870

119863119899

119862HC119898

)

119899

119862HC119898minus1

(1 + 119870

119886 [H+])119898

(19)



119863





3(S) (22)


(23)


and119870


119870

11=

C11(1 + 119870

119886 [H+])

119862HC [S](24)

119870

21=

C21(1 + 119870

119886 [H+])

119862HCC11(25)

119870

31=

C31(1 + 119870

119886 [H+])

119862HCC21(26)

119870

12=

C12

C11[S]

(27)

C11 C21 C31 and C



119862HC = C11+ 2C21+ 3C31+ C12

=

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

2119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

3119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

(28)

[S] = [S]inminus (C11+ C21+ C31+ 2C12)

= [S]inminus (

119870

11[S] 119862HC

[1 + 119870

119886 [H+]]

+

119870

11119870

21[S] 1198622HC

[1 + 119870

119886 [H+]]2

+

119870

11119870

21119870

31[S] 1198623HC

[1 + 119870

119886 [H+]]3

+

2119870

11119870

12[S]2

119862HC

[1 + 119870

119886 [H+]]

)

(29)


11

119870

21 11987031


11

C21 C31 and C




119885 =

119862HC

[S]in

(30)


11) as given

by (31)119885

1 minus 119885

= 119870

11[HC] (31)


119885

119898 minus 119885

= 119870

1198981[HC]119898 (32)


) as

119870

chem119863

=


119862HC

(33)


119863


119870

total119863

= ]119870diluent119863

+ 119870

chem119863

(34)




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




[(HC)119898(S)119899] = 119862HC minus ]119862

diluentHC

(35)


119870

119898119899[HC]119898 =



diluentHC )]

119899 (36)


119883119884119885 = 119883119884119885

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585 (37)


log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119886120572 + 119887120573 + ℎ120575H + 119890120585

(38)


119863


10

119870



log10

119870

119863= log10

119870

119863

0

+ 119904 (120587

lowast

+ 119889120575) + 119887120573 + 119886120572(39)


119863) In


119878119875

12= 119883

1119878119875

1+ (1 minus 119883

1) 119878119875

2 (40)


2=

1 minus 119883


1is




119886of acid








Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table2Ex

tractantdilu

entsystem

forthe

separatio

nof

carboxylicacidsb

yreactiv

eextraction

kinetic

studies

SLnu

mber

Carboxylic

acid

Extractant

Dilu

ent

Parameters

Find

ings

References

1PenicillinG

AmberliteLA

-2Ke

rosene

Agitatio


etween

twoim

misc

iblesolutio

nspHof

aqueou

sph


concentration

Arateequatio

nforthe

masstransferw

asprop

osed

with


rateconstantsa

s1198961

=16

4L3molminus2

sminus1

and119896

2

=656times10minus5

Lsminus1

respectively

[49]

2Citric

TOA

iso-decanoland

n-paraffin

Con

centratio

nsof

acid

andam

inea

ndspeedof

agitatio

nFo

rmalelem

entary

kinetic

mod

elprop

osed

andreactio

nkinetic

sevaluated

[50]

3PenicillinG

AmberliteLA

-2Ke

rosene

andn-bu

tyl

acetate

Aqueou

sand

organicp

hase

compo

sitionspHand

temperature


faqu

eous

layerd

iffusion

interfa

cialchem

ical

reactio

nandorganiclayer

diffu

sionwere

quantitatively

determ

ined

[51]

4Tartaric

TIOA

iso-decanoland

kerosene

Con

centratio

nsof

acidamineand

iso-decanol

Mod

ified

Lang

muirisotherm

was

prop

osed

andkinetic

parameters

interpretedby

aformalele

mentary

kinetic

mod

el

[52]

5Lactic

Aliq

uat336

Oleylalcoho

l

Initiallactatea

ndextractant

concentrations

inextractio

ninitial

chlorid

eandextractant-la

ctatec

omplex

concentrations

instrip

ping

Extractio

nandstr

ipping

kinetic

swere


hthe

organic-ph

asefi

lmwas

determ

ined

asthe

rate-determiningste

p

[53]

6Ph

enylacetic

Alamine3

36Ke

rosene

andMIBK

Acid

andam

inec

oncentratio

nvolume

ratio

ofph

asesand

stirrer

speed

Intrinsic

kineticsw

ered

escribedthe

reactio

nfoun

dto

bezero

orderin

Alamine3


with

arateconstant

of09sminus1

[54]

7PenicillinG

AmberliteLA

-2Ke

rosene

Acid

andam

inec

oncentratio

nandpH

Disp

ersedliq

uid-liq

uidextractio

nsyste

mprop

osedD

anckwertand

Biot

nosu

sed

todeterm

iner

ates

tep

[55]




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




[119878]



1 Very slowltlt1

120572[HC]119898 120572[S]119899 None 120572 119881org


None

3 Fastgtgt1

120572[HC](119898+1)2 120572[S]1198992 None None



None


119881aq119889119862org

119889119905

= 119896

119871119860

119888(119862

lowast




ln(119862

lowast

org

119862

lowast


119896

119871119860

119888

119881org119905 (42)



119871)


119877HC0 =119881org

119860

119888

(

119889119862HCorg

119889119905

)

119905=0

(43)


119877HC0 = 11989612057210158401205731015840 [HC]120572

1015840

[S]120573

1015840

(44)





119867119886 =

radic

(2 (120572

1015840

+ 1)) 119896

12057210158401205731015840 [HC]

1205721015840minus1

[S]1205731015840

119863HC

119896

119871

(45)



119879

radic

Ψ119872

120578 (forall

acid)

06

(46)

119863HC = 10minus11

119879

radic

119872

120578 (forall

diluentforall

acid)

13

(47)



Φ =

119877HC0

119896

119871119862

lowast

org (48)



References






























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

review article status of the reactive extraction as a...

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