review article effects of surfactants on the rate of chemical...

Review ArticleEffects of Surfactants on the Rate ofChemical Reactions

B Samiey1 C-H Cheng2 and J Wu2

1 Department of Chemistry Faculty of Science Lorestan University 68137-17133 Khoramabad Iran2Department of Chemical Engineering Ryerson University Toronto ON Canada M5B 2K3

Correspondence should be addressed to B Samiey babsamieyyahoocom

Received 13 August 2014 Accepted 16 October 2014 Published 30 December 2014

Academic Editor Tomokazu Yoshimura

Copyright copy 2014 B Samiey et alThis is an open access article distributed under theCreativeCommonsAttribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Surfactants are self-assembled compounds that depend on their structure and electric charge can interact as monomer ormicelle with other compounds (substrates) These interactions which may catalyze or inhibit the reaction rates are studied withpseudophase cooperativity and stoichiometric (classical) models In this review we discuss applying these models to studysurfactant-substrate interactions and their effects on Diels-Alder redox photochemical decomposition enzymatic isomerizationligand exchange radical and nucleophilic reactions

1 Introduction

Self-organized assemblies such as micelles can change therates of chemical and enzymatic reactions Effects of micellesof surfactants on these reactions can be attributed to theirelectrostatic and hydrophobic interactions with reactantsSurfactants are amphiphilic organic compounds containingboth hydrophobic groups (their tails) and hydrophilic groups(their heads) Thus a surfactant molecule contains both awater insoluble component and a water soluble componentThe tail of most surfactants consists of a hydrocarbonchain Surfactants are classified into four types (1) Anionicsurfactants such as sodium dodecyl sulfate (SDS) containanionic functional groups at their head that is sulfate sul-fonate and phosphate (2) Cationic surfactants for examplecetyltrimethylammonium bromide (CTAB) have cationicfunctional groups such as quaternary ammonium cation(3) Zwitterionic surfactants have one cationic center andone anionic center both attached to the same molecule Thecationic part is based on primary secondary or tertiaryamines or quaternary ammonium cations and the anionicpart can be for example sulfonate and carboxylate [1] (4)Nonionic surfactants (such as Triton X-100) do not ionizein an aqueous solution because their hydrophilic groups are

nondissociable Gemini surfactants (such as gemini 16-2-16)are a relatively new class of amphiphilic molecules containingtwo head groups and two aliphatic chains linked by a rigidor flexible spacer [2] They show greatly enhanced surfactantproperties relative to the corresponding monovalent surfac-tants Figure 1

A micelle is an aggregate of surfactant molecules dis-persed in a liquid colloid Micelles form only when theconcentration of surfactant is greater than the critical micelleconcentration (CMC) This type of micelle is known as anormal-phase micelle (oil-in-water micelle) In a nonpolarsolvent a reverse micelle (water-in-oil micelle) forms inwhich the hydrophilic groups of surfactant are sequesteredin the micelle core and the hydrophobic groups extend awayfrom the center [3] Figure 2

2 Classification of Kinetic Models

In this study three models used to study kinetics of reactionsin the presence of surfactants are discussed

21 Pseudophase Model The pseudophase (or pseudophaseion-exchange (PPIE)) model was first introduced by Mengerand Portnoy [4] in 1967 to study effects of surfactant micelles

Hindawi Publishing CorporationJournal of ChemistryVolume 2014 Article ID 908476 14 pageshttpdxdoiorg1011552014908476

2 Journal of Chemistry

CTAB SDS

O

Tween-80

Gemini 16-2-16

Septonex Brij 97Brminus

BrminusO

O O

SO Na

H3C

OHO

n

N+

O

O

CH3(CH2)6CH2CH=CHCH2(CH2)6CH2(OCH2CH2)10OH

Triton X-100 (TX-100) n = 9-10Triton X-305 (TX-305) n = 30 (avg)

Triton X-405 (TX-405) n = 40C16H33ndashN+(CH3)2ndashN+(CH3)2ndashC16H33

w(CH2CH2O)OH (OCH2CH2)xOH

(OCH2CH2)yOH O

O(OCH2CH2)zC17H33

+N

Where sum of w x y and z = 20

Figure 1 Structures of several surfactants

Hydrophilic head

Aqueoussolution

Hydrophobic tail

(a)

H2O

Oil

(b)

Figure 2 Typical structures of (a) micelle and (b) reverse micelle

on the chemical reaction rates They considered surfactantmicelles as a pseudophase that can interact with some or allof reactants (or substrates) can further dissolve substratesand can alter the reaction rate of substrates Therefore thismodel cannot study the interaction between the substrate andsurfactant molecules below the CMC With respect to thedefinition of micelle as a pseudophase there is no stoichio-metric ratio between the substrate and surfactant moleculesfor the presence of this interactionThe distribution constantof each substrate between solvent andmicelle is defined as thebinding constant of the substrate with amicelleThe substrate

(119878) distributes between the solvent and a micelle (119863119899) as

follows

DnS SDn

Products Products

+

kw km

KS

(1)

where 119896119908and 119896119898are the observed rate constants in the solvent

and micelles respectively 119870119878is the association constant of

Journal of Chemistry 3

the substrate with the micelles In this model it is assumedthat a single equilibrium relation thus one119870

119878value is applied

within thewhole surfactant concentration rangeOn the basisof the above model the following relation for the observedrate constant (119896obs) has been derived

1

(119896obs minus 119896119908)=

1

(119896119898minus 119896119908)+

1

(119896119898minus 119896obs)119870119878 ([119863] minus CMC)

(2)

where [119863] is the surfactant concentration Depending on thenumber of substrates and other compounds (such as salts)relations of 119896obs can be written as different forms

22 Cooperativity Model Piszkiewicz presented cooperativ-ity model [5] in 1976 analogous to the enzyme-catalyzedreactions This model is used only for reactions catalyzedby surfactants He assumed that a micelle (119863

119899) forms a

noncovalent complex (119863119899119878) with the substrate (119878) before the

catalysis takes place

119863119899+ 119878119870

larrrarr 119863119899119878

119863119899119878119896119898

997888rarr products

1198781198960

997888rarr products

(3)

where 119870 is the association constant of the micelle-substratecomplex 119896

119898is the rate constant for micelle-catalyzed reac-

tion and 1198960is the rate constant for the reaction in the

absence of micelle Similar to pseudophasemodel this modelassumed that there is only one equilibrium relation thus one119870119878value within the whole surfactant concentration range

The 119896obs at any concentration of surfactant is given by

119896obs =1198960+ 119896119898119870 (([119863] minus CMC) 119899)

1 + 119870 (([119863] minus CMC) 119899) (4)

where 119899 is the number of surfactant molecules per micelleThus this model can study interactions between the substrateand surfactant molecules above the CMC An alternativecooperativity model analogous to the Hill model applied toenzyme-catalyzed reactions was proposed that the substrateand surfactant molecules aggregate to form micelles 119863

119899119878

which may then react to yield product

119899119863 + 119878119870119863

larrrarr 119863119899119878

119863119899119878119896119898

997888rarr products

1198781198960

997888rarr products

(5)

The model gives the following rate equation

log[(119896obs minus 1198960)

(119896119898minus 119896obs)

] = 119899 log [119863]119905minus log119870

119863 (6)

where 119870119863

is the dissociation constant of micellizedsurfactant-substrate complex and [119863]

119905is the total surfactant

60

70

80

90

100

110

120

000 001 001 002 002 003

[surfactant] (mM)

sc

kob

s(M

minus1m

inminus1)

R + n1SK1harr RSn1

RSn1 + n2SK2harr RSn1+n2

Figure 3 Typical equilibrium relations between reactant andsurfactant molecules in a two-region system

concentration 119899 is known as the cooperativity index and is ameasure of the association of additional surfactant moleculesto an aggregate in the whole surfactant concentration rangeIf 119899 value is greater than one the cooperativity of interactionis positive and if its value is less than one the cooperativityof interaction is negative and if its value is equal to 1 theinteraction is noncooperative

23 Stoichiometric Model Samiey introduced the stoichio-metric (classical) model [6] in 2004 In the stoichiometricmodel [6] it is assumed that in each range of surfac-tant concentration the surfactant and substrate can bindtogether and an equilibrium relation exists The surfactantconcentration in which the equilibrium relation between theadded surfactant (119878) and the species already present in thesolution (119877) ends and a new equilibrium relation between theadded surfactant and the compound resulted from previousequilibrium relation (119877119878

1198991) starts which is called ldquosubstrate-

surfactant complex formation pointrdquo (or abbreviated as scpoint) and is as follows

119877 + 11989911198781198701

larrrarr 1198771198781198991

(in the first region)

1198771198781198991+ 11989921198781198702

larrrarr 1198771198781198991+1198992

(in the second region)

(7)

The CMC value of a surfactant is also a sc point and theremay be some sc points higher and lower than CMC aswell The range of surfactant concentration which covers anequilibrium relation is named ldquoregionrdquo Figure 3

Surfactant molecules either monomeric or micellar canbind to the substrate molecules Micelles can bind to the sub-strate by one or more number of their surfactant moleculesThus we can obtain the stoichiometric ratios and bindingconstants of interactions between surfactant molecules andwith the substrate in various surfactant concentration rangesThe following equation holds for each equilibrium relation[6]

ln 1198961015840 = 119888 minus119864119878

119877119879[119878]119905 (8)


where 1198961015840 119888 [119878]119905119877 and119879 are the rate constant in the presence

of surfactant ln 119896 (at first region) or ln 119896sc (for other regions)total surfactant concentration universal gas constant andabsolute temperature respectively 119864

119878is the catalytic or inhi-

bition energy of reaction at constant temperature and varioussurfactant concentrations 119896sc is the 119896obs in the starting ofeach region except region one and 119896 is the 119896obs in theabsence of surfactants Equation (8) is introduced as ldquoSamieyequationrdquo [6] and determines the concentration range of eachregion If the reaction rate decreases with the increase ofsurfactant concentration the sign of 119864

119878is positive and is

called ldquoinhibition energyrdquo and if the reaction rate increaseswith increasing the surfactant concentration the sign of119864119878is negative and is named ldquocatalytic energyrdquo at constant

temperature and various surfactant concentrations [6] Theunit of 119864

119878is kJ (mol molar (surfactant))minus1 In this model it is

assumed that in each region one substrate molecule 119877 bindsto 119899molecules of surfactant and we have

119877 + 119899119878119870

larrrarr 119877119878119899 (9)

where 119870 is the binding constant of the substrate-surfactantinteraction in each region According to stoichiometricmodel these interactions contain two types Type I is theinteraction of which surfactant molecules have an inhibitoryeffect on the reaction rate yielding a decreased reactionrate Type II is the interaction of which surfactant moleculesexert a catalytic effect on the reaction rate resulting inan increased reaction rate [6] Some surfactants show anincreased reaction rate in a certain concentration range (typeI) and a decreased reaction rate in the other range (typeII) The 119896obs which indicates the interaction between onespecies of substrate with one kind of the surfactant is speciesdependent and is related to the surfactant concentration asfollows [6]

119896obs =

119896 + 119896119878119870 [119878]119899

119905

1 + 119870 [119878]119899

119905

(region one)

119896sc + 119896119878119870([119878]119905 minus [sc])119899

1 + 119870 ([119878]119905minus [sc])119899

(all other regions)

(10)

where 119896 and 119896sc are the 119896obs in the absence of surfac-tant (beginning of the first region) and at each sc pointrespectively 119896

119878is the reaction rate constant in the substrate-

surfactant complex and is greater than reaction rate inpure solvent (119896) but when the surfactant has an inhibitoryeffect 119896

119878= 0 Going from one region to the next one

if 1198701119899 value (the average binding constant of interactionbetween one substrate molecule and one surfactant moleculein each region) increases the cooperativity of interactionis positive and if 1198701119899 value decreases the cooperativity ofinteraction is negative The total binding constant (119870119894tot) and

total stoichiometric ratio (119899119894tot) values for each substrate inthe 119894th region can be obtained from following equations

119870119894

tot = 1198701 sdot sdot sdot 119870119894minus1119870119894 =119894

prod119895=1

119870119895

119899119894

tot = 1198991 + sdot sdot sdot + 119899119894minus1 + 119899119894 =119894

sum119895=1

119899119895

(11)

Also using this model we can study interactions of mixedmicelles with substrate molecules and calculate the stoi-chiometric ratios and binding constants of their surfactantmolecules with substrate molecules [6]

24 Comparison of Stoichiometric Cooperativity and PPIEModels (1) In the PPIE model the colloidal particles of sur-factant (after cmc) are considered as an ion exchanger and thebinding of substrate to them is considered like the partition ofa substrate between the two phases (micelle and solvent) Inthe PPIE and cooperativitymodels the stoichiometric ratio ofsurfactant (as micelle) to the substrate is 1 1 and there is oneaverage binding constant for substrate-surfactant compoundin the whole surfactant concentration range while in thestoichiometric model the stoichiometric ratio of surfactant(either micellar or monomeric) to the substrate is n 1 and ineach region there is a new equilibrium relation and thereforea new binding constant a new stoichiometric ratio andnegative or positive cooperativity [6](2)The PPIE and cooperativity models is not applicable

in the region before the cmc point of surfactant but inthe stoichiometric model the binding of substrate to themonomeric surfactant is considered(3) In the PPIE and cooperativity models for the cases in

which the reaction rate increases in one range of surfactantconcentration and decreases in another range it is assumedthat in average there is one type of interaction between surfac-tant and substrate molecules Therefore there is one bindingconstant for whole range of the surfactant concentrationsBut in these cases in the stoichiometric model it is assumedthat the substrate molecules have different interactions withsurfactant molecules and the reaction is catalyzed in one ormore regions and inhibited in another region(s) Thereforethe binding constants are not identical in different regions(4) In the PPIE and cooperativity models it is assumed

that the rate constant in micelle (119896119898) is not usually equal to

zero But in the stoichiometric model it is assumed that therate constant in micelle for catalysis of reaction is more thanthe rate constant of free substrate and in the state of inhibitionof reaction it is equal to zero(5) In the PPIE and cooperativity models only one sc

point is assumed which corresponds to the cmc of surfactantBut in the stoichiometric model there are various sc pointsincluding cmc(6) In the PPIE and cooperativity models the binding

constant and stoichiometric ratio of single type substrate-surfactant interaction aremeasured But in the stoichiometricmodel we can evaluate the stoichiometric ratios and bindingconstants ofmultiple type substrate-surfactant interactions ineach region [6]


(7) In the stoichiometric model K values calculated foreach region obey the Vanrsquot Hoff equation whereas the bindingconstants obtained from the PPIE and cooperativity modelsare not so in most of the cases

3 Change in the Chemical Reaction Rate inthe Presence of Surfactants

Interaction of surfactant molecules with substrates can resultin decreasing or increasing the reaction rate or changing theyield of reaction and sometimes these surfactant moleculesact as reactants In this section we discuss the role of temper-ature and cosolvents on the interactions between surfactantsand substrates as well as the effects of head group chainlength charge and concentration of surfactants in a seriesof reactions for example Diels-Alder redox photochemicaldecomposition enzymatic isomerization ligand exchangeradical and nucleophilic reactions Furthermore this sectionalso discusses the potential role of surfactants as a reactant

31 Diels-Alder Reactions The Diels-Alder reaction is anorganic chemical reaction (specifically a [4 + 2] cycloaddi-tion) between a conjugated diene and a substituted alkenecommonly termed the dienophile to form a substitutedcyclohexene system Because the majority of the diene anddienophile intermolecularDiels-Alder reactions have a ratherpronounced nonpolar character an efficient binding of bothsubstrates to micelles is anticipated This would imply thatthe effective reaction volume for the Diels-Alder reaction issignificantly reduced leading to micellar catalysis [7]

A study on the reaction of cyclopentadienewith a series ofdienophiles shows the roles of charge and substituent groupsin their interaction with surfactants [8ndash12]

In the reaction of acridizinium bromide (a cationicdienophile) with cyclopentadiene a 10-fold reaction rate isinduced by anionic SDS micelles whereas nonionic TX-100and cationic 1-N-dodecyl-4-methylpyridinium bromide haveonly modest effects on the reaction rate [8] The efficientcatalysis by SDS most likely results from electrostaticallyenhanced binding of the dienophile to the micelles [8 9] Butthe reaction rate of 12-dicyanoethylene with cyclopentadi-enedecreases with the increase of SDS concentrations whichis due to weak interactions between 12-dicyanoethylene andSDS micelles [10] It seems to point toward the Stern regionof the micelles as the prominent site for this Diels-Alderreaction

Rispens and Engberts [11] studied the reaction rate ofcyclopentadiene with a series of N-substituted maleimidesin SDS micellar media They observed that up to 30mMof SDS the reaction rate of cyclopentadiene with N-methylmaleimide is constant while its rate with N-butyl and N-benzyl substituted maleimideincreases with the size of sub-stituent group This is because the butyl and benzyl sub-stituent groups lead to deeper solubilization ofN-substitutedmaleimide in the SDS micelle compared to the methyl-substituted compound Evidence suggests that the reaction inthe micellar phase mainly takes place in the region betweenthe core and the Stern layer thereby still experiencing apolar environment In all the above-mentioned cases the

apolar cyclopentadiene might be expected to mainly residein the apolar micellar core It was observed that if theSDS concentration is more than 30mM the reaction ratedecreases Pseudophase model considers just one kind ofinteraction occurring between SDS and substrate moleculeswithin thewhole SDS concentration range and calculated that119896119898value is less than 119896

119908 However it seems that pseudophase

model fails to show that 119896119898is greater than 119896

119908when the SDS

concentration is less than 30mMSimonyan and Gitsov [12] studied the first Diels-Alder

reaction performed in an aqueous medium with highlyhydrophobic compounds such as fullerene (C

60) as the

dienophile and anthracene or tetracene as the dienesrespectively The reactions were performed in nanocon-tainers constructed by self-assembly of linear-dendriticamphiphilic copolymers Figure 4 Surfactants can also affectthe endoexoselectivity [13] regioselectivity [14] and enan-tioselectivity [15] of the Diels-Alder reactions

32 Redox Reactions The catalytic effects of SDS NaBDS(anionic gemini surfactant) and mixed surfactants (SDS +NaBDS) on the oxidation rate of D-fructose by alkalinechloramine-T have been investigated [16] The observedcatalytic effect of mixed micelle on the oxidation rate wasalways less than the combination of the catalytic effectsof two individual surfactants suggesting an antagonism(negative synergism) in the mixed micelle The antagonismhas also been confirmed by determining the CMC and theinteraction parameter (120573119898) of mixed micelle According tothe pseudophasemodel119870

119878and 119896119898values of interaction ofD-

fructose with SDS were 82Mminus1 and 165 times 10minus4 sminus1 and thoseof D-fructose with NaBDS were 400Mminus1 and 179 times 10minus4 sminus1at 35∘C respectively

The catalytic effects of zwitterionic micellar solutions ofSB3-14 and SB3-16 on the redox reaction of Brminus + BrO

3

minus

have been studied using the pseudophase model [17] The119870119878and 119896

119898values of BrO

3

minus with SB3-14 were 310Mminus1 and124 times 10minus3 sminus1 and those of BrO

3

minus with SB3-16 were 3100Mminus1and 099 times 10minus3 sminus1 respectively In the presence of the sameconcentrations of surfactants the reaction rate of using SB3-16 is less than that of using SB3-14 It seems that deepersolubilization of BrO

3

minus in SB3-16 micelles decreases itsreaction rate with Brminus

Vanadium (V) oxidation of D-glucose was studied inthe presence of CPC SDS and TX-100 [18] CPC inhibitsthe reaction while SDS and TX-100 accelerate the reactionto different extents The observed effects were studied bythe cooperativity model and were explained by consideringthe hydrophobic and electrostatic interactions between thesurfactants and substrates Similarly oxidation reactions ofCe(IV) [19] or oxyanions such as CrO

4

2minus [20 21] andMnO4

minus

[22] with organic compounds have been studied in thepresence of surfactants

Surfactants can affect the nucleation and growth kinetics[23 24] and the reduction [25] of nanocompounds Forinstance colloidal silver particles in the nanometer size rangewere synthesized in ethanol by the reduction of AgNO

3

with nonionic surfactants Brij 97 and Tween 80 [25] Themain conclusion is that surfactants reduce silver ions to the


OO

O O

OO O

O

OO

OO

O

OO

O

OO

OOO

OO

OO

O

O O

O

O O

O

OO

OO O

O

OO

OO O

O

O

O O O

O

O

OO

OO

O

O O

OOO

O OO

O

OOOO

O O

OO

O

OO

OO O

OO

OO

O OOO

OO

O

O

OO

O

O

O O O O O O OO

OO O O

OO

OO

OO

O OO

OO

O OO

O

OO

O

OO O

OOO

O

OO O

OOOO

OO

OO

O

OOO

OO

O

O O OO

OOO

OO

OO

OOO

OOOO

OO

OO

OOOOO

OOOOO

O

OOO

O O

OOO

OO

O

OOOOO

OO

OOHO

O

OO

HO

OO

OOH O

OO

O OH

OOOHO

O

OO O

OOO

OO

OOO

OO

OO

O O O OO

OO

HO

H2O

H2O

H2O

H2OH2O

H2ODiels-Alderproducts

Solid

Solid

+

+

+

Figure 4 Mass transfer in and out of the micellar nanoreactor entity [12]


neutral state through the oxidation of oxyethylene groupsinto hydroperoxides Surfactantmolecules subsequently wereadsorbed onto the surface of particles promoting stericstabilization This adsorption permits also the transfer of theparticles into nonpolar solvents through a dry state where noparticle aggregation occurs

As reported [26ndash29] the electron transfer reaction wasstudied in the presence of surfactants The electron transferreaction between [Co(NH

3)5(N-cyanopiperidine)]3+ pen-

taammine(N-cyanopiperidine)-cobalt(III) and hexacyano-ferrate(II) has been studied in aqueous solutions [29] Thealteration of electron transfer rate constant in the presenceof SDS Brij 35 and TX-100 has been investigated at 2982 KThe rationalization of the experimental data was assistedby the use of the Marcus theory on electron transfer Theconclusion is that the micellar effects on the electron transferrate constant can be explained by considering the micelles asa special background electrolyte with a high electric chargeand a strong power of hydration

Surfactants can affect the time stability of cation radicals[30 31] As reported the time stability of diethazine cationradical (DE+∙) decreased in the presence of surfactants [30]Below the CMC Septonex (a cationic surfactant) monomerscannot interact with DE+∙ and do not affect the degradationrate Above the CMC the DE+∙ degradation is catalyzed bySeptonex micelles that are able to bind to DE+∙ particlesthrough hydrophobic interactions without associating withH+ ions The DE+∙ degradation occurring in the micellarpseudophase relatively poor in H+ ions is therefore muchfasterThe effect of nonionic surfactant TX-305 is similar withthe cationic surfactant but less significant On the other handthe associations of DE+∙ with SDS premicelle aggregateswhich do not bind to H+ ions formed below the CMC of SDSand the rate of DE+∙ decomposition quickly increases withthe increase in SDS concentration For the concentrations ofSDS higher than the CMC DE+∙ radicals are bound to thenegatively charged surface of micelles together with H+ ionsTherefore the DE+∙ decomposition reaction is inhibited athigher surface local H+ activity and the DE+∙ degradationrates decrease

33 Photochemical Reactions The solutions of 3-(4-chlo-rophenyl)-ll-dimethylurea (monuron) were photolyzed inaqueousmedia containing nonionic surfactants [32]TheTX-100 TX-405 TMN-6 and TMN-10 were used to elucidatethe influences of aryl- and alkyl-substituted polyoxyethyleneglycol surfactants Concentrations of all surfactant solutionswere above each individual CMC Samples were examinedunder oxygenated and nonoxygenated conditions Thepresence of surfactants enhances the degradation rate ofmonuron eliminates ring hydroxylation reactions andpromotes the reductive dechlorination reaction Monuronis adsorbed on the lyophilic surface or into lipophilic coreof micelles Similar to that observed for the photolysis ofnitroaromatic [33] and 2-chlorophenol [34] compounds theresults indicate that these photochemical reactions occur inthe organic phase of the micelles rather than the aqueousphase of the solvent In addition to the interaction with

substrate surfactants can sometimes act as an additionalsource of hydrogen for the reaction [35 36]

The TiO2photosensitized oxidation of 4-dodecyloxyben-

zyl alcohol which is water insoluble was investigated inaqueous solutions of anionic cationic and nonionic surfac-tants [37] The reaction which is practically absent in wateris greatly enhanced by several surfactants at concentrationshigher than CMC and the effect is strongly dependent onthe nature of the surfactant The increase of surfactantconcentration leads to more substrate molecules solubilizedin micelles which are transported close to the TiO

2particle

surface where the photooxidation reaction takes place Aftera certain concentration which varies with the nature of thesurfactant the presence of competitive partition of comicel-lized 4-dodecyloxybenzyl alcohol (substrate) between TiO

2

surface (where the reaction occurs) and bulk solvent tends todiminish the beneficial kinetic effect of surfactant

ForNNN1015840N1015840-tetramethylbenzidine solubilized inmixedmicelles of C12E6SDS or C12E6DTAC the electron spin-echo and electron spin resonance spectra of photogeneratedcations show that the photoionization yield depends on thesign of net charge of the mixed micelle and on the strengthof the photocation-water interaction [38] It is found that thephotoyield is enhanced by the presence of mixed micelleswith a net positive charge probably due to the fact thatelectron escaping from the micelle is facilitated in cationicmicelles

Photogalvanic effects were studied in photogalvanic cellscontaining SDS as a surfactant EDTA as a reductant andazur-B as a photosensitizer [39]The used SDS solubilizes thedye more easily and stabilizes the system and may increasethe probability of charge transfer between the surfactantand the dye in the system compared to the tunneling ofphotoelectrons from themicellar phase to the aqueous phase

34 Decomposition Reactions In the presence of SDSmicelles 1-naphthalenediazonium (ArN+

2) is incorporated

into the micellar aggregates given the estimated 119870119878of

290Mminus1 and 119896119898= 9 times 10minus4 sminus1 It shows that a significant

fraction of 1-naphthalenediazonium is incorporated intothe micellar pseudophase at low-surfactant concentrationswhere it undergoes thermal decomposition in the Stern layer[40]

Brinchi et al [41] studied the decarboxylation ofanionic 6-nitrobenzisoxazole-3-carboxylate (6-NBIC) and its5-methyl derivative (6-NBIC-5-Me) in the presence of aseries of several cationic cetyltrialkylammonium bromidesurfactants including CTAB CTEAB CTPAB and CTBABFigure 5

Cationic micelles of cetyltrialkylammonium bromidefacilitate the decarboxylation of both 6-NBIC and 6-NBIC-5-Me by decreasing activation enthalpies It was observed thatthe reaction rates and119870

119878values increase with the head group

size of surfactants It was also observed that the reactionrate increases with the surfactant concentration when thesurfactant concentration is low and then decreases withfurther increase in the surfactant concentration It seemsthat with increase in the surfactant concentration differentinteractions are involved between substrate and surfactants


R RR

O2N O2NO2N

N N

OO O

O

minus

O

CC

N

C

O

minus

Ominus

+ CO2

Figure 5 Decarboxylation of substrates 6-NBIC and 6-NBIC-5-Me [41]

NNNHN NH

OHO

OO P

NO2BrminusBrminus Brminus

BrminusH2O

H2O

H2O

H2O

H2O

OHminus

OHminus

OHminus

Stern layer

Bulk phase

+

+ ++

OminusOH∙

Figure 6 Catalytic cleavage of 2-hydroxypropyl p-nitrophenylphosphate by Zn(II) complex in the Stern layer of gemini 16-2-16micelles [45]

molecules in these two cases But using the pseudophasemodel only one 119896

119898and 119870

119878value are calculated for the

interaction of substrate with each of these surfactants in thewhole range of surfactant concentration

On the other hand surfactant chain length can affectits interaction with substrates [42 43] The kinetics studyof the acid hydrolysis of anionic N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) in media containing differentcationic micellar aggregates LTAB TTAB CTAB and 120573-cyclodextrin (120573-CD) [42] shows that the119870

119878values of interac-

tion between MNTS and surfactants increase with the chainlength of surfactants As reported [44] using cationic geminisurfactants with longer chain length increases the cleavage ofcarboxylate ester

Jiang et al [45] studied effects of increasing in both chargeand chain length of surfactantThey investigated the cleavageof phosphate diesters mediated by Zn(II) complex inmicellarsolutions of cationic gemini 16-2-16 andCTAB Figure 6Theyobserved that the cleavage rate of diester using CTAB isonly about 40 of that using gemini 16-2-16 micelles undercomparable conditions This is due to the doubling of chainlength and charge of gemini 16-2-16 compared to CTAB

35 Enzymatic Reactions Polyphenol oxidase (PPO)extracted from table beet leaves [46] potato leaf [47]persimmon fruit [48] and 120572-chymotrypsin [49] was

activated in the presence of SDS SDSDS mixed micellesSDS and DTAB respectively and their activities dueto denaturation are decreased at higher surfactantconcentrations The kinetic parameters of interactionof two samples of PPO with surfactants [46 47] werecalculated by the stoichiometric model [6] Results showthat the positive cooperativity is observed during theseinteractions But activity of PPO extracted from beet root[50] is increased in the applied SDS concentration rangeand its kinetic parameters were calculated using the Hillequation that is similar to (6) used in the cooperativitymodel For soluble PPO the values of Hill coefficient (119899

119867)

of tyramine dopamine L-tyrosine and L-DOPA substrateswere 22 27 39 and 42 indicating that the number ofSDS molecules needed for activation is higher for morehydrophilic substrates These results corroborate that theability of SDS to activate the enzyme involves a limitedconformational change due to the binding of small amountsof SDS [51] The access of hydrophobic substrates to theactive site is favored since the first molecules of SDS arebound to the enzyme while hydrophilic substrates require adeeper change for full access (activity)

Enzymatic synthesis using lipase in organic solventshas several advantages [52 53] The solubility of nonpolarsubstrates is increased in organic solvents and the reactiondirection can be shifted to favor synthesis over hydrolysisHowever like all other natural enzymes organic solventseasily denature lipase To avoid the deactivation of enzymein organic media modification of enzyme surface by coatingit with surfactants has been studied [52] For example itwas observed that whereas the unmodified lipase from Bcepacia was insoluble in tert-butyl alcohol the propyleneglycol monostearate-coated lipase exhibited an enhancedsolubility in tert-butyl alcohol at the reaction temperature[52] The formation of reverse micelles stabilized the enzymein the organic solvent otherwise the enzyme would havebeen denatured by removing the surrounding microaqueouslayer Figure 7

36 Isomerization Ligand Exchange and Radical ReactionsGille et al [54] studied the thermal cis-trans-isomerizationof 441015840-nitroanilinoazobenzene dye in the presence SDSTX-100 and Igepal CA-520 In microheterogeneouswatersurfactant solutions isomerization rate constantvalues of selected azo dyes were strongly dependent on theconcentrations of SDS and TX-100 in water and varied withthe composition of bicontinuous microemulsions of Igepal


S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)

Glycerol(substrate 2)

Triacylglycerol(substrate 1)

Diacylglycerol(product 1)

Monoacylglycerol(product 2)

+

1sim2nm

Hydrophilic phaseLipophilic phase

Reversed micelleSurfactant

Figure 7 Schematic representation of AOTisooctane reversed micellar system [53]

CA-520heptanewater The large spread of isomerizationrate constants is in part due to varying microviscosity

They showed that the trans-azo dyes have a constantbalancing average microenvironment in the watersurfactantinterface layer in a wide range of micelle concentrationsThe isomerization rates of cis-isomer decrease by an order ofmagnitude with increasing the surfactant concentration inpart due to increasing microviscosity

The rate of ligand substitution reaction betweenFe(CN)

5H2O3minus and pyrazine is decreased in the presence of

CTAB [55] The kinetic data showed that both nonmicellizedand micellized CTAB are operative kinetically and interactwith Fe(CN)

5H2O3minus The pseudophase model can be used to

study this interaction only for CTAB concentrations above itsCMCand the calculated119870

119878and 119896119898were 260Mminus1 and 127 sminus1

respectivelyThis strong interaction competes with the ligandsubstitution reaction Similarly the study of substitutionrate of 4-cyanopyridine (4-CNpy) in Fe(CN)(4-CNpy)3minusby S2O8

2minus in the presence of CTAB and TTAB shows thatthe longer the chain length of surfactant is the more thereaction rates decreased [56] On the other hand it wasobserved that the reaction rate is not influenced by changesin the concentration of TX-100 and SDS This observationshows the importance of preliminary electrostatic and then

hydrophobic interactions of surfactants and substrates onthe ligand substitution reaction rate

Graciani et al [57] showed that the rate of substitutionof bipyridine (bpy) in Fe(CN)

4(bpy)2minus by S

2O8

2minus increases inthe presence of zwitterionic surfactant SB3-14 The moderateinteraction of positive headgroup of SB3-14 with substratesincreases their concentrations on the surface of SB3-14micelles and increases the reaction rate Here the authorscalculated binding constants of SB3-14 to Fe(CN)

4(bpy)2minus

and S2O8

2minus separately using kinetic data in the pseudophasemodel and using conductometry data respectively

Emulsion polymerization is an example for radical reac-tions in the presence of surfactants [58ndash60] Tang et al[60] studied copolymerization of methyl methacrylate butylacrylate and styrene in combination with a water-solubleanionic monomer (methacrylic acid or acrylic acid) and anonionic monomer (N-methylol acrylamide) The emulsifiersurfactant DSB at a level greater than its CMCgenerated par-ticle nuclei by micelle nucleation and controlled the particlesize particle size distribution and the rate of polymerization

37 Nucleophilic Reactions Studies show that the reactionrates of a number of nucleophilic reactions of hydroxideion with neutral compounds in the presence of cationic


Table 1 Parameters obtained from stoichiometric model for interaction of ME2+ with SDS at 283ndash303K [83]

119879 (K) Region sc(mM)

119896sc(Mminus1minminus1) Samiey equation 119864

119878log119870 119899 Cooperativity

2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133

darrminus2nd 097 3900 ln 1198961015840 = minus43805[SDS]

119905+ 406 10307 422 149

darrminus3rd 480 751 ln 1198961015840 = minus8773[SDS]

119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128

Dimension of 119864119878is in kJ (molmolar(surfactant))minus1 Dimension of SDS concentration in the Samiey equation is in M Dimension of119870 is in Mminus119899

surfactants first increase and then decrease with increasein surfactant concentration [61ndash68] and the catalytic effectof cationic surfactants increases with the increase of theirchain length [61 66 68] Also the reaction rate decreasesin the presence of anionic surfactants [63 65 67 69] anddecreases with increase in the surfactant chain length [70] Inthe former case the formation of positively charged cationicsurfactantsubstrate complex promotes the reaction rate andthen the interaction of more cationic surfactant molecules(having hydrophobic chains) with substrate decreases itsinteraction with negatively charged hydroxide ions Butin the pseudophase model only one kind of interaction isconsidered within the whole surfactant concentration rangeand only one binding constant is calculated In the lattercase the interaction of anionic surfactants with neutralsubstrates increases the electronic repulsion between theresulted complex and hydroxide ions

On the other hand the reaction rates of a number ofnucleophiles (other than hydroxide ion) with neutral [71ndash73]and anionic [74ndash79] substrates are increased in the presenceof cationic surfactants It was observed that the increase in thechain length of cationic surfactants [75] and adding TX-100[79] to the reaction media decreases the reaction rate Alsoresults show that adding organic cosolvents [76ndash78] to thesurfactant-contained media further decreases the reactionrate compared to that in the presence of surfactant onlyTheseobservations are due to the added organic cosolvents increasethe CMC of surfactants and the interaction of TX-100 withcationic surfactants (in their mixedmicelles) competes for itsinteraction with substrate molecules

In addition to interaction with substrate molecules sur-factants sometimes can form ion pairs with them As anexample it has been reported that SDS attacks cationic crystalviolet dye and causes the formation of dye-surfactant ion pair[80]

As reported reactions of some triphenylmethane dyeswith hydroxide ion (fading) in the presence of surfac-tants have been studied by cooperativity pseudophase andstoichiometric models [81ndash84] For comparing the resultsobtained from these models the fading rate of cationicmethyl green (ME2+) dye in the presence of SDS [83] isstudied According to the stoichiometric model in the used

concentration range of SDS there are three regions (or threekinds of interactions) at each temperature and the data ofcollected below theCMCare used in the calculations Table 1

Preliminary electrostatic and then hydrophobic inter-actions of SDS with ME2+ decrease the positive charge ofME2+ and decrease the reaction rate of ME2+ with hydroxideion With the increase of SDS concentration the reactionrate decreases and thus 119896

119878= 0 in each region Also from

the first to the third region the impact of SDS on thereaction rate decreases and thus 119864

119878values decrease At each

temperature from the first to the third region the (119870)1119899values in each region decrease and thus the cooperativityof reaction is negative Reactions in the first and secondregions are exothermic and those in the third region areendothermic resulting in a negative value of Δ119867tot Usingthe data of different regions of SDS and TX-100 the dataof fading reaction of ME2+ in their mixtures was analyzedand stoichiometric ratios and binding constants of themwithME2+ were calculated

According to the cooperativity model the interaction ofSDS with ME2+ is endothermic and 119896

119878= 0 and at all

temperatures the cooperativity of process is positive Thedata of fading reaction in the presence of SDS did not fitto the pseudophase model This example shows that theobtained results are not similar to each other due to thedifferent presumptions used in pseudophase cooperativityand stoichiometric models

4 Conclusions

This review discusses effects of different kinds of surfactantsin a series of chemical reactions including Diels-Alder redoxphotochemical decomposition enzymatic isomerizationligand exchange radical and nucleophilic reactions Theseinteractions were catalyzed or inhibited via the change in thedielectric constant of microenvironment orand the charge ofsubstrate molecules As observed in all discussed examplespreliminary electrostatic and then hydrophobic interactionsoccur between surfactants and substrate molecules Sub-stratesurfactant interactions are studied using pseudophasecooperativity and stoichiometric models Due to different


assumptions made in these models results obtained fromthem may be different from each other

Acronyms and Proprietary Names forSome Surfactants

Brij 35 Dodecyltricosaethylene glycol etherBrij 97 Polyoxyethylene-10-oleyl etherCPC N-Cetylpyridinium chlorideCTAB Cetyltrimethylammonium bromideC12E6 Hexakis(ethylene glycol)monododecyl

etherCTEAB Cetyltriethylammonium bromideCTPAB Cetyltrin-propylammonium bromideCTBAB Cetyltrin-butylammonium bromideDS Dodecanesulfonic acidDSB Sodium alkylated diphenyl ether

disulfonateDTAC Dodecyltrimethylammonium chlorideGemini 16-2-16 Bis(hexadecyl dimethyl ammonium)

ethane bromideIgepal CA-520 p-Isooctylphenyl-pentaethylenglycoletherLTAB Lauryltrimethylammonium bromideNaBDS Sodium salt of bis(1-dodecenylsuccinamic

acid)SB3-14 N-Tetradecyl-NN-dimethyl-3-ammonio-

1-propanesulfonateSB3-16 N-Hexadecyl-NN-dimethyl-3-ammonio-

1-propanesulfonateSDS Sodium dodecyl sulfateSeptonex Carbethopendecinium bromideTMN-10 268-Trimethyl-4-

nonyloxypolyethyleneoxyethanolTMN-6 2-(268-Trimethyl-4-nonyloxy)ethanolTriton X-100 Polyethylene glycol [4-(1133-tetramethyl

butyl)phenyl] etherTTAB Tetradecyltrimethylammonium bromideTween-80 Polyethylene oxide sorbitan monooleate

Conflict of Interests

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

References

[1] D Myers Surfactant Science and Technology John Wiley andSons Hoboken NJ USA 2006

[2] F M Menger and C A Littau ldquoGemini surfactants synthesisand propertiesrdquo Journal of the American Chemical Society vol113 no 4 pp 1451ndash1452 1991

[3] httpenwikipediaorgwikiMicelle[4] F M Menger and C E Portnoy ldquoOn the chemistry of reactions

proceeding inside molecular aggregatesrdquo Journal of the Ameri-can Chemical Society vol 89 no 18 pp 4698ndash4703 1967

[5] D Piszkiewicz ldquoMicelle catalyzed reactions are models ofenzyme catalyzed reactions which show positive homotropicinteractionsrdquo Journal of the American Chemical Society vol 98no 10 pp 3053ndash3055 1976

[6] B Samiey K Alizadeh M A Moghaddasi M F Mousavi andN Alizadeh ldquoStudy of kinetics of bromophenol blue fadingin the presence of SDS DTAB and Triton X-100 by classicalmodelrdquo Bulletin of the Korean Chemical Society vol 25 no 5pp 726ndash736 2004

[7] S Otto and J B F N Engberts ldquoDiels-Alder reactions in micel-lar mediardquo in Reactions and Synthesis in Surfactant Systems JTexter Ed chapter 9 pp 247ndash263 Marcel Dekker New YorkNY USA 2011

[8] G K Van Wel J W Wijnen and J B F N Erigberts ldquoSolventeffects on a diels-alder reaction involving a cationic dieneconsequences of the absence of hydrogen-bond interactions foraccelerations in aqueous mediardquo Journal of Organic Chemistryvol 61 no 25 pp 9001ndash9005 1996

[9] E B Mubofu and J B F N Engberts ldquoSurfactant-assistedspecific-acid catalysis of Diels-Alder reactions in aqueousmediardquo Journal of Physical Organic Chemistry vol 20 no 10pp 764ndash770 2007

[10] I Hunt and C D Johnson ldquoDials-Alder reaction of fumaroni-trile and cyclopentadiene in water the influence of cosolutesrdquoJournal of the Chemical Society Perkin Transactions 2 no 7 pp1051ndash1056 1991

[11] T Rispens and J B Engberts ldquoMicellar catalysis of Diels-Alderreactions substrate positioning in the micellerdquo The Journal ofOrganic Chemistry vol 67 no 21 pp 7369ndash7377 2002

[12] A Simonyan and I Gitsov ldquoLinear-dendritic supramolecularcomplexes as nanoscale reaction vessels for ldquogreenrdquo chemistryDiels-Alder reactions between fullerene C

60and polycyclic

aromatic hydrocarbons in aqueousrdquo Langmuir vol 24 no 20pp 11431ndash11441 2008

[13] R Braun F Schuster and J Sauer ldquo(4+2)-cycloadditionen inMicellen ein vergleich des produktspektrums und der reak-tionsgeschwindigkeit mit reaktionen in Losungrdquo TetrahedronLetters vol 27 no 11 pp 1285ndash1288 1986

[14] G B van de Langkruis and J B F N Engberts ldquoMicellareffects on the reaction of (arylsulfonyl)alkyl arenesulfonateswith hydroxide ion 1 Microenvironmental and substituenteffects in the stern layer of cationic micellesrdquo Journal of OrganicChemistry vol 49 no 22 pp 4152ndash4157 1984

[15] S Otto F Boccalatti and J B F N Engberts ldquoA chiral Lewis-acid-catalyzed Diels-Alder reaction Water-enhanced enantios-electivityrdquo Journal of the AmericanChemical Society vol 120 no17 pp 4238ndash4239 1998

[16] N Kambo and S K Upadhyay ldquoAntagonism in (conventionalanionic-gemini anionic) mixed micelle catalyzed oxidation ofD-fructose by alkaline chloramine-Trdquo International Journal ofChemical Kinetics vol 41 no 2 pp 123ndash132 2009

[17] A RodrıguezM delMar GracianiMMunoz andM LMoyaldquoStudy of the bromide oxidation by bromate in zwitterionicmicellar solutionsrdquo International Journal of Chemical Kineticsvol 32 no 6 pp 388ndash394 2000

[18] B Saha S Sarkar and K M Chowdhury ldquoMicellar effect onquinquivalent vanadium ion oxidation of D-glucose in aqueousacid media a kinetic studyrdquo International Journal of ChemicalKinetics vol 40 no 5 pp 282ndash286 2008

[19] A K Das M Islam and R Bayen ldquoStudies on kineticsand mechanism of oxidation of D-sorbitol and D-mannitolby cerium (IV) in aqueous micellar sulfuric acid mediardquoInternational Journal of Chemical Kinetics vol 40 no 8 pp445ndash453 2008


[20] A M A Morshed and Z Khan ldquoRole of manganese(II)micelles and inorganic salts on the kinetics of the redox reac-tion of L- sorbose and chromium(VI)rdquo International Journal ofChemical Kinetics vol 35 no 11 pp 543ndash554 2003

[21] K Hartani and Z Khan ldquoMicellar catalysis on the redoxreaction of glycolic acid with chromium(VI)rdquo InternationalJournal of Chemical Kinetics vol 33 no 6 pp 377ndash386 2001

[22] M A Malik F M Al-Nowaiser N Ahmad and Z KhanldquoKinetics of MnOminus

4oxidation of succinic acid in aqueous

solution of cetyltrimethylammonium bromiderdquo InternationalJournal of Chemical Kinetics vol 42 no 12 pp 704ndash712 2010

[23] Z Zaheer and Rafiuddin ldquoNucleation and growth kineticsof silver nanoparticles prepared by glutamic acid in micellarmediardquo International Journal of Chemical Kinetics vol 44 no10 pp 680ndash691 2012

[24] R G Chaudhuri and S Paria ldquoGrowth kinetics of sulfurnanoparticles in aqueous surfactant solutionsrdquo Journal of Col-loid and Interface Science vol 354 no 2 pp 563ndash569 2011

[25] L M Liz-Marzan and I Lado-Tourino ldquoReduction and stabi-lization of silver nanoparticles in ethanol by nonionic surfac-tantsrdquo Langmuir vol 12 no 15 pp 3585ndash3589 1996

[26] P V Subba Rao G Krishna Rao K Ramakrishna G Rambabuand A Satyanarayana ldquoKinetics of some electron-transferreactions of iron(III)-221015840-bipyridyl complex Micellar effect ofsodium dodecyl sulphaterdquo International Journal of ChemicalKinetics vol 29 no 3 pp 171ndash179 1997

[27] K C Rajanna K N Reddy U U Kumar and P K Sai PrakashldquoA kinetic study of electron transfer from l-ascorbic acid tosodium perborate and potassium peroxy disulphate in aqueousacid and micellar mediardquo International Journal of ChemicalKinetics vol 28 no 3 pp 153ndash164 1996

[28] T Majumdar H K Mandal P Kamila and A MahapatraldquoInfluence of polymerndashsurfactant interactions on the reactivityof the Co119868119868119868-Fe119868119868 redox couplerdquo Journal of Colloid and InterfaceScience vol 350 no 1 pp 212ndash219 2010

[29] A Rodrıguez M Del Mar Graciani R Balahura and M LMoya ldquoMicellar effects on the electron transfer reaction withinthe ion pair [(NH

3)5Co(N-cyanopiperidine)]3+[Fe(CN)

6]4minusrdquo

The Journal of Physical Chemistry vol 100 no 42 pp 16978ndash16983 1996

[30] I Nemcova and I Jelınek ldquoThe influence of some surfactantsand inorganic salts on the stability of diethazine cation radicalrdquoChemical Papers vol 47 no 3 pp 149ndash152 1993

[31] V B Gawandi S N Guha H Mohan and J P Mittal ldquoKineticand redox characteristics of semireduced species derived fromphenosafranine in homogeneous aqueous and sodium dodecylsulfate micellar mediardquo International Journal of Chemical Kinet-ics vol 34 no 1 pp 56ndash66 2002

[32] F S Tanaka R GWien and E RMansager ldquoEffect of nonionicsurfactants on the photochemistry of 3-(4-chlorophenyl)-11-dimethylurea in aqueous solutionrdquo Journal of Agricultural andFood Chemistry vol 27 no 4 pp 774ndash779 1979

[33] R A Larson C T Jafvert F Bosca K A Marley and P LMiller ldquoEffects of surfactans on reduction and photolysis (gt290nm) of nitroaromatic compoundsrdquo Environmental Science andTechnology vol 34 no 3 pp 505ndash508 2000

[34] Z Shi M E Sigman M M Ghosh and R DabestanildquoPhotolysis of 2-chlorophenol dissolved in surfactant solutionsrdquoEnvironmental Science and Technology vol 31 no 12 pp 3581ndash3587 1997

[35] C Y Kwan and W Chu ldquoReaction mechanism of photoreduc-tion of 24-dichlorophenoxyacetic acid in surfactant micellesrdquo

Industrial and Engineering Chemistry Research vol 44 no 6pp 1645ndash1651 2005

[36] W K Choy W Chu and C Y Kwan ldquoPhotochemical degra-dation of 246-trichlorophenol in the presence of a nonionicsurfactant pH control on reaction kineticsrdquo Journal of Environ-mental Engineering vol 133 no 6 pp 641ndash645 2007

[37] M Bettonia L Brinchib T Del Giaccob et al ldquoSurfactanteffect on titanium dioxide photosensitized oxidation of 4-dodecyloxybenzyl alcoholrdquo Journal of Photochemistry and Pho-tobiology A vol 229 no 1 pp 53ndash59 2012

[38] P Baglioni E Rivara-Minten C Stenland and L Kevan ldquoPho-toionization of NNN1015840N1015840-tetramethylbenzidine in a mixedmicelle of ionic and nonionic surfactants electron spin-echomodulation and electron spin resonance studiesrdquo Journal ofPhysical Chemistry vol 95 no 24 pp 10169ndash10172 1991

[39] R C Meena G Singh N Tyagi and M Kumari ldquoStudiesof surfactants in photogalvanic cellsmdashNaLs-EDTA and azur-Bsystemrdquo Journal of Chemical Sciences vol 116 no 3 pp 179ndash1842004

[40] C Bravo-Diaz M J Pastoriza-Gallego S Losada-BarreiroV Sanchez-Paz and A Fernandez-Alonso ldquoDediazoniationof 1-naphthalenediazonium tetrafluoroborate in aqueous acidand in micellar solutionsrdquo International Journal of ChemicalKinetics vol 40 no 6 pp 301ndash309 2008

[41] L Brinchi R Germani L Goracci G Savelli N Spreti and Pdi Profio ldquoTemperature effects upon aqueous micellar-assisteddecarboxylation of 6-nitrobenzisoxazole-3-carboxylate and its5-methyl derivativerdquo Journal of Colloid and Interface Sciencevol 298 no 1 pp 426ndash431 2006

[42] I Fernandez L Garcıa-Rıo P Herves J C Mejuto J Perez-Juste and P Rodrıguez-Dafonte ldquo120573-Cyclodextrin-micellemixed systems as a reaction medium Denitrosation of N-methyl-N- nitroso -p-toluenesulfonamiderdquo Journal of PhysicalOrganic Chemistry vol 13 no 10 pp 664ndash669 2000

[43] L Brinchi R Germani E Braccalenti N Spreti MTiecco and G Savelli ldquoAccelerated decarboxylation of 6-nitrobenzisoxazole-3-carboxylate in imidazolium-based ionicliquids and surfactant ionic liquidsrdquo Journal of Colloid andInterface Science vol 348 no 1 pp 137ndash145 2010

[44] B Kumar D Tikariha K K Ghosh N Barbero and PQuagliotto ldquoKinetic study on effect of novel cationic dimericsurfactants for the cleavage of carboxylate esterrdquo Journal ofPhysical Organic Chemistry vol 26 no 8 pp 626ndash631 2013

[45] W Jiang B Xu Q Lin et al ldquoCleavage of phosphate diestersmediated by Zn(II) complex in Gemini surfactant micellesrdquoJournal of Colloid and Interface Science vol 311 no 2 pp 530ndash536 2007

[46] J Escribano J Cabanes and F Garcıa-Carmona ldquoCharacterisa-tion of latent polyphenol oxidase in table beet effect of sodiumdodecyl sulphaterdquo Journal of the Science of Food andAgriculturevol 73 no 1 pp 34ndash38 1997

[47] A Sanchez-Ferrer F Laveda and F Garcıa-Carmona ldquoSub-strate-dependent activation of latent potato leaf polyphenoloxidase by anionic surfactantsrdquo Journal of Agricultural and FoodChemistry vol 41 no 10 pp 1583ndash1586 1993

[48] E Nunez-Delicado M M Sojo F Garcıa-Carmona and ASanchez-Ferrer ldquoPartial purification of latent persimmon fruitpolyphenol oxidaserdquo Journal of Agricultural and Food Chem-istry vol 51 no 7 pp 2058ndash2063 2003

[49] K K Ghosh and S K Verma ldquoEffects of head group of cationicsurfactants on the hydrolysis of p-nitrophenyl acetate catalyzed


by a-chymotrypsinrdquo International Journal of Chemical Kineticsvol 41 no 6 pp 377ndash381 2009

[50] F Gandıa-Herrero M Jimenez-Atienzar J Cabanes F Garcıa-Carmona and J Escribano ldquoDifferential activation of a latentpolyphenol oxidase mediated by sodium dodecyl sulfaterdquo Jour-nal of Agricultural and Food Chemistry vol 53 no 17 pp 6825ndash6830 2005

[51] B M Moore and W H Flurkey ldquoSodium dodecyl sulfateactivation of a plant polyphenoloxidase Effect of sodiumdodecyl sulfate on enzymatic and physical characteristics ofpurified broad bean polyphenoloxidaserdquo Journal of BiologicalChemistry vol 265 no 9 pp 4982ndash4988 1990

[52] H-J Hsieh G R Nair and W-T Wu ldquoProduction of ascorbylpalmitate by surfactant-coated lipase in organic mediardquo Journalof Agricultural and Food Chemistry vol 54 no 16 pp 5777ndash5781 2006

[53] K M Park C W Kwon S J Choi et al ldquoThermal deactiva-tion kinetics of Pseudomonas fluorescens lipase entrapped inAOTisooctane reverse micellesrdquo Journal of Agricultural andFood Chemistry vol 61 no 39 pp 9421ndash9427 2013

[54] K Gille H Knoll and K Quitzsch ldquoRate constants of thethermal cis-trans isomerization of azobenzene dyes in solventsacetonewater mixtures and in microheterogeneous surfactantsolutionsrdquo International Journal of Chemical Kinetics vol 31 no5 pp 337ndash350 1999

[55] M Del Mar Graciani M A Rodrıguez andM L Moya ldquoStudyof the ligand substitution reaction Fe(CN)

5H2O3minus + pyrazine in

micellar solutionsrdquo International Journal of Chemical Kineticsvol 29 no 5 pp 377ndash384 1997

[56] G FernandezMDMGraciani A RodrıguezMMunoz andM LMoya ldquoStudy of the reaction Fe(CN )

5(4-CNpy)3minus+ S

2O2minus8

in aqueous salt and micellar solutionsrdquo International Journal ofChemical Kinetics vol 31 no 2-3 pp 229ndash235 1999

[57] M D M Graciani A Rodrıguez M Munoz and M L MoyaldquoStudy of the reaction Fe(CN)

4(bpy)2minus + S

2O2minus8

in sulfobetaineaqueous micellar solutionsrdquo International Journal of ChemicalKinetics vol 33 no 4 pp 225ndash231 2001

[58] C S Chern ldquoEmulsion polymerization mechanisms and kinet-icsrdquoProgress in Polymer Science vol 31 no 5 pp 443ndash486 2006

[59] E Ozdeger E D Sudol M S El-Aasser and A Klein ldquoRoleof the nonionic surfactant Triton X-405 in emulsion polymer-ization III Copolymerization of styrene and n-butyl acrylaterdquoJournal of Polymer Science Part A Polymer Chemistry vol 35no 17 pp 3837ndash3846 1997

[60] L Tang J Yang S Zhang and Y Wu ldquoEmulsifier-minoremulsion copolymerization of BA-MMA-St-MAA (or AA)-NMArdquo Journal of Applied Polymer Science vol 92 no 5 pp2923ndash2929 2004

[61] B Kumar K K Ghosh and P R Dafonte ldquoComparativestudy of the cationic surfactants and their influence on thealkaline hydrolysis of acetylsalicylic acidrdquo International Journalof Chemical Kinetics vol 43 no 1 pp 1ndash8 2011

[62] N Singh K K Ghosh J Marek and K Kuca ldquoHydrolysisof carboxylate and phosphate esters using monopyridiniumoximes in cationic micellar mediardquo International Journal ofChemical Kinetics vol 43 no 10 pp 569ndash578 2011

[63] F F Al-Blewi H A Al-Lohedan M Z A Rafiquee and Z AIssa ldquoKinetics of hydrolysis of procaine in aqueous andmicellarmediardquo International Journal of Chemical Kinetics vol 45 no 1pp 1ndash9 2013

[64] S K Gangwar and M Z A Rafiquee ldquoKinetics of the alkalinehydrolysis of fenuron in aqueous and micellar mediardquo Interna-tional Journal of Chemical Kinetics vol 39 no 11 pp 638ndash6442007

[65] S K Gangwar and M Z A Rafiquee ldquoKinetics of the alkalinehydrolysis of isoproturon in CTAB and NaLS micellesrdquo Inter-national Journal of Chemical Kinetics vol 39 no 1 pp 39ndash452007

[66] A Cuenca ldquoSurfactant effects on the reaction of 2-(4-cyano-phenoxy)-quinoxaline with hydroxide ionrdquo International Jour-nal of Chemical Kinetics vol 38 no 8 pp 510ndash515 2006

[67] M N Al-Shamary H A Al-Lohedan M Z A Rafiquee andZ A Issa ldquoMicellar effects on aromatic nucleophilic substitu-tion by the ANRORC mechanism Hydrolysis of 2-chloro-35-dinitropyridinerdquo Journal of Physical Organic Chemistry vol 25no 8 pp 713ndash719 2012

[68] A S Al-Ayed M S Ali H A Al-Lohedan A M Al-Sulaimand Z A Issa ldquoEffect of alkyl chain length head group andnature of the surfactant on the hydrolysis of 13-benzoxazine-24-dione and its derivativesrdquo Journal of Colloid and InterfaceScience vol 361 no 1 pp 205ndash211 2011

[69] A Malpica M Calzadilla and H Linares ldquoMicellar effect uponthe reaction of hydroxide ion with coumarinrdquo InternationalJournal of Chemical Kinetics vol 30 no 4 pp 273ndash276 1998

[70] G Astray A Cid J A Manso J C Mejuto O Moldes andJ Morales ldquoInfluence of anionic and nonionic micelles uponhydrolysis of 3-hydroxy-carbofuranrdquo International Journal ofChemical Kinetics vol 43 no 8 pp 402ndash408 2011

[71] B Kumar M L Satnami K K Ghosh and K Kuca ldquoCompar-ative studies on reaction of bis(p-nitrophenyl) phosphate and120572-nucleophiles in cationic micellar mediardquo Journal of PhysicalOrganic Chemistry vol 25 no 10 pp 864ndash871 2012

[72] K K Ghosh J Vaidya and M L Satnami ldquoThe 120572-effect inmicelles nucleophilic substitution reaction of 119901-nitrophenylacetate with 119873-phenylbenzohydroxamate ionrdquo InternationalJournal of Chemical Kinetics vol 38 no 1 pp 26ndash31 2006

[73] K K Ghosh S Bal S Kolay and A Shrivastava ldquoCom-parative nucleophilic reactivities in carboxylate phosphinateand thiophosphate esters cleavagerdquo Journal of Physical OrganicChemistry vol 21 no 6 pp 492ndash497 2008

[74] S K Sar N Rathod and P K Pandey ldquoNucleophilic deben-zoylation of p-nitrophenyl benzoate in cationicmicellarmediardquoInternational Journal of Chemical Kinetics vol 42 no 2 pp 106ndash112 2010

[75] M M Mohareb K K Ghosh and R M Palepu ldquoKinetics ofthe reaction ofmethyl 4-nitrobenzenesulfonate + Br- in ethanolamine based surfactantsrdquo International Journal of ChemicalKinetics vol 38 no 5 pp 303ndash308 2006

[76] MMunozMDelMarGraciani A Rodrıguez andM LMoyaldquoEffects of alcohols on micellization and on the reaction methyl4-nitrobenzenesulfonate + Brminus in cetyltrimethylammoniumbromide aqueous micellar solutionsrdquo International Journal ofChemical Kinetics vol 36 no 12 pp 634ndash641 2004

[77] M Del Mar Graciani A Rodrıguez G Fernandez MMunoz and M L Moya ldquoStudy of the reaction of methyl4-nitrobenzenesulfonate and Brminus in waterndashglycerol cationicmicellar solutionsrdquo International Journal of Chemical Kineticsvol 40 no 12 pp 845ndash852 2008

[78] M A Rodrıguez M Munoz M del Mar Graciani GFernandez and M L Moya ldquoEffects of head group size on


the reaction methyl 4-nitrobenzenesulfonate + Brminus in water-ethylene glycol cetyltrialkylammonium bromide micellar solu-tionsrdquo International Journal of Chemical Kinetics vol 39 no 6pp 346ndash352 2007

[79] G Fernandez A Rodrıguez M del Mar Graciani MMunoz and M L Moya ldquoStudy of the reaction methyl4-nitrobenzene-sulfonate +Cl- in mixed hexadecyltrimethyl-ammonium chloride-Triton X-100 micellar solutionsrdquo Interna-tional Journal of Chemical Kinetics vol 35 no 2 pp 45ndash51 2003

[80] B Samiey and F Ashoori ldquoKinetics of crystal violet fading in thepresence of TX-100 DTAB and SDSrdquo Acta Chimica Slovenicavol 58 no 2 pp 223ndash232 2011

[81] B Samiey and A R Toosi ldquoKinetics study of malachite greenfading in the presence of TX-100 DTAB and SDSrdquo Bulletin ofthe Korean Chemical Society vol 30 no 9 pp 2051ndash2056 2009

[82] B Samiey andM R Dargahi ldquoKinetics of brilliant green fadingin the presence of TX-100 DTAB and SDSrdquo Reaction KineticsMechanisms and Catalysis vol 101 no 1 pp 25ndash39 2010

[83] B Samiey and Z Dalvand ldquoKinetics of methyl green fading inthe presence of TX-100 DTAB and SDSrdquo Bulletin of the KoreanChemical Society vol 34 no 4 pp 1145ndash1152 2013

[84] B Samiey and Z Dalvand ldquoStudy of fuchsin acid fading inmicellar mediardquo International Journal of Chemical Kinetics vol46 no 11 pp 651ndash661 2014

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


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


CTAB SDS

O

Tween-80

Gemini 16-2-16

Septonex Brij 97Brminus

BrminusO

O O

SO Na

H3C

OHO

n

N+

O

O

CH3(CH2)6CH2CH=CHCH2(CH2)6CH2(OCH2CH2)10OH

Triton X-100 (TX-100) n = 9-10Triton X-305 (TX-305) n = 30 (avg)

Triton X-405 (TX-405) n = 40C16H33ndashN+(CH3)2ndashN+(CH3)2ndashC16H33

w(CH2CH2O)OH (OCH2CH2)xOH

(OCH2CH2)yOH O

O(OCH2CH2)zC17H33

+N

Where sum of w x y and z = 20

Figure 1 Structures of several surfactants

Hydrophilic head

Aqueoussolution

Hydrophobic tail

(a)

H2O

Oil

(b)

Figure 2 Typical structures of (a) micelle and (b) reverse micelle

on the chemical reaction rates They considered surfactantmicelles as a pseudophase that can interact with some or allof reactants (or substrates) can further dissolve substratesand can alter the reaction rate of substrates Therefore thismodel cannot study the interaction between the substrate andsurfactant molecules below the CMC With respect to thedefinition of micelle as a pseudophase there is no stoichio-metric ratio between the substrate and surfactant moleculesfor the presence of this interactionThe distribution constantof each substrate between solvent andmicelle is defined as thebinding constant of the substrate with amicelleThe substrate

(119878) distributes between the solvent and a micelle (119863119899) as

follows

DnS SDn

Products Products

+

kw km

KS

(1)

where 119896119908and 119896119898are the observed rate constants in the solvent

and micelles respectively 119870119878is the association constant of





1

(119896obs minus 119896119908)=

1

(119896119898minus 119896119908)+

1


(2)



119899) forms a



119863119899+ 119878119870

larrrarr 119863119899119878

119863119899119878119896119898

997888rarr products

1198781198960

997888rarr products

(3)






119896obs =1198960+ 119896119898119870 (([119863] minus CMC) 119899)

1 + 119870 (([119863] minus CMC) 119899) (4)


119899119878


119899119863 + 119878119870119863

larrrarr 119863119899119878

119863119899119878119896119898

997888rarr products

1198781198960

997888rarr products

(5)


log[(119896obs minus 1198960)

(119896119898minus 119896obs)

] = 119899 log [119863]119905minus log119870

119863 (6)

where 119870119863



60

70

80

90

100

110

120

000 001 001 002 002 003

[surfactant] (mM)

sc

kob

s(M

minus1m

inminus1)

R + n1SK1harr RSn1







119877 + 11989911198781198701

larrrarr 1198771198781198991


1198771198781198991+ 11989921198781198702

larrrarr 1198771198781198991+1198992


(7)



ln 1198961015840 = 119888 minus119864119878

119877119879[119878]119905 (8)











119877 + 119899119878119870

larrrarr 119877119878119899 (9)


119896obs =

119896 + 119896119878119870 [119878]119899

119905

1 + 119870 [119878]119899

119905

(region one)

119896sc + 119896119878119870([119878]119905 minus [sc])119899

1 + 119870 ([119878]119905minus [sc])119899

(all other regions)

(10)







119870119894


prod119895=1

119870119895

119899119894


sum119895=1

119899119895

(11)




















119908when the SDS



60) as the






3

minus


119898values of BrO

3


3


3



4


minus



3



OO

O O

OO O

O

OO

OO

O

OO

O

OO

OOO

OO

OO

O

O O

O

O O

O

OO

OO O

O

OO

OO O

O

O

O O O

O

O

OO

OO

O

O O

OOO

O OO

O

OOOO

O O

OO

O

OO

OO O

OO

OO

O OOO

OO

O

O

OO

O

O

O O O O O O OO

OO O O

OO

OO

OO

O OO

OO

O OO

O

OO

O

OO O

OOO

O

OO O

OOOO

OO

OO

O

OOO

OO

O

O O OO

OOO

OO

OO

OOO

OOOO

OO

OO

OOOOO

OOOOO

O

OOO

O O

OOO

OO

O

OOOOO

OO

OOHO

O

OO

HO

OO

OOH O

OO

O OH

OOOHO

O

OO O

OOO

OO

OOO

OO

OO

O O O OO

OO

HO

H2O

H2O

H2O

H2OH2O


Solid

Solid

+

+

+












2particle


2





2) is incorporated









R RR

O2N O2NO2N

N N

OO O

O

minus

O

CC

N

C

O

minus

Ominus

+ CO2


NNNHN NH

OHO

OO P


BrminusH2O

H2O

H2O

H2O

H2O

OHminus

OHminus

OHminus

Stern layer

Bulk phase

+

+ ++

OminusOH∙



119898and 119870









119867)





S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)





+

1sim2nm
















4(bpy)2minus by S

2O8


4(bpy)2minus

and S2O8









2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





1

(119896obs minus 119896119908)=

1

(119896119898minus 119896119908)+

1


(2)



119899) forms a



119863119899+ 119878119870

larrrarr 119863119899119878

119863119899119878119896119898

997888rarr products

1198781198960

997888rarr products

(3)






119896obs =1198960+ 119896119898119870 (([119863] minus CMC) 119899)

1 + 119870 (([119863] minus CMC) 119899) (4)


119899119878


119899119863 + 119878119870119863

larrrarr 119863119899119878

119863119899119878119896119898

997888rarr products

1198781198960

997888rarr products

(5)


log[(119896obs minus 1198960)

(119896119898minus 119896obs)

] = 119899 log [119863]119905minus log119870

119863 (6)

where 119870119863



60

70

80

90

100

110

120

000 001 001 002 002 003

[surfactant] (mM)

sc

kob

s(M

minus1m

inminus1)

R + n1SK1harr RSn1







119877 + 11989911198781198701

larrrarr 1198771198781198991


1198771198781198991+ 11989921198781198702

larrrarr 1198771198781198991+1198992


(7)



ln 1198961015840 = 119888 minus119864119878

119877119879[119878]119905 (8)











119877 + 119899119878119870

larrrarr 119877119878119899 (9)


119896obs =

119896 + 119896119878119870 [119878]119899

119905

1 + 119870 [119878]119899

119905

(region one)

119896sc + 119896119878119870([119878]119905 minus [sc])119899

1 + 119870 ([119878]119905minus [sc])119899

(all other regions)

(10)







119870119894


prod119895=1

119870119895

119899119894


sum119895=1

119899119895

(11)




















119908when the SDS



60) as the






3

minus


119898values of BrO

3


3


3



4


minus



3



OO

O O

OO O

O

OO

OO

O

OO

O

OO

OOO

OO

OO

O

O O

O

O O

O

OO

OO O

O

OO

OO O

O

O

O O O

O

O

OO

OO

O

O O

OOO

O OO

O

OOOO

O O

OO

O

OO

OO O

OO

OO

O OOO

OO

O

O

OO

O

O

O O O O O O OO

OO O O

OO

OO

OO

O OO

OO

O OO

O

OO

O

OO O

OOO

O

OO O

OOOO

OO

OO

O

OOO

OO

O

O O OO

OOO

OO

OO

OOO

OOOO

OO

OO

OOOOO

OOOOO

O

OOO

O O

OOO

OO

O

OOOOO

OO

OOHO

O

OO

HO

OO

OOH O

OO

O OH

OOOHO

O

OO O

OOO

OO

OOO

OO

OO

O O O OO

OO

HO

H2O

H2O

H2O

H2OH2O


Solid

Solid

+

+

+












2particle


2





2) is incorporated









R RR

O2N O2NO2N

N N

OO O

O

minus

O

CC

N

C

O

minus

Ominus

+ CO2


NNNHN NH

OHO

OO P


BrminusH2O

H2O

H2O

H2O

H2O

OHminus

OHminus

OHminus

Stern layer

Bulk phase

+

+ ++

OminusOH∙



119898and 119870









119867)





S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)





+

1sim2nm
















4(bpy)2minus by S

2O8


4(bpy)2minus

and S2O8









2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of











119877 + 119899119878119870

larrrarr 119877119878119899 (9)


119896obs =

119896 + 119896119878119870 [119878]119899

119905

1 + 119870 [119878]119899

119905

(region one)

119896sc + 119896119878119870([119878]119905 minus [sc])119899

1 + 119870 ([119878]119905minus [sc])119899

(all other regions)

(10)







119870119894


prod119895=1

119870119895

119899119894


sum119895=1

119899119895

(11)




















119908when the SDS



60) as the






3

minus


119898values of BrO

3


3


3



4


minus



3



OO

O O

OO O

O

OO

OO

O

OO

O

OO

OOO

OO

OO

O

O O

O

O O

O

OO

OO O

O

OO

OO O

O

O

O O O

O

O

OO

OO

O

O O

OOO

O OO

O

OOOO

O O

OO

O

OO

OO O

OO

OO

O OOO

OO

O

O

OO

O

O

O O O O O O OO

OO O O

OO

OO

OO

O OO

OO

O OO

O

OO

O

OO O

OOO

O

OO O

OOOO

OO

OO

O

OOO

OO

O

O O OO

OOO

OO

OO

OOO

OOOO

OO

OO

OOOOO

OOOOO

O

OOO

O O

OOO

OO

O

OOOOO

OO

OOHO

O

OO

HO

OO

OOH O

OO

O OH

OOOHO

O

OO O

OOO

OO

OOO

OO

OO

O O O OO

OO

HO

H2O

H2O

H2O

H2OH2O


Solid

Solid

+

+

+












2particle


2





2) is incorporated









R RR

O2N O2NO2N

N N

OO O

O

minus

O

CC

N

C

O

minus

Ominus

+ CO2


NNNHN NH

OHO

OO P


BrminusH2O

H2O

H2O

H2O

H2O

OHminus

OHminus

OHminus

Stern layer

Bulk phase

+

+ ++

OminusOH∙



119898and 119870









119867)





S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)





+

1sim2nm
















4(bpy)2minus by S

2O8


4(bpy)2minus

and S2O8









2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of












119908when the SDS



60) as the






3

minus


119898values of BrO

3


3


3



4


minus



3



OO

O O

OO O

O

OO

OO

O

OO

O

OO

OOO

OO

OO

O

O O

O

O O

O

OO

OO O

O

OO

OO O

O

O

O O O

O

O

OO

OO

O

O O

OOO

O OO

O

OOOO

O O

OO

O

OO

OO O

OO

OO

O OOO

OO

O

O

OO

O

O

O O O O O O OO

OO O O

OO

OO

OO

O OO

OO

O OO

O

OO

O

OO O

OOO

O

OO O

OOOO

OO

OO

O

OOO

OO

O

O O OO

OOO

OO

OO

OOO

OOOO

OO

OO

OOOOO

OOOOO

O

OOO

O O

OOO

OO

O

OOOOO

OO

OOHO

O

OO

HO

OO

OOH O

OO

O OH

OOOHO

O

OO O

OOO

OO

OOO

OO

OO

O O O OO

OO

HO

H2O

H2O

H2O

H2OH2O


Solid

Solid

+

+

+












2particle


2





2) is incorporated









R RR

O2N O2NO2N

N N

OO O

O

minus

O

CC

N

C

O

minus

Ominus

+ CO2


NNNHN NH

OHO

OO P


BrminusH2O

H2O

H2O

H2O

H2O

OHminus

OHminus

OHminus

Stern layer

Bulk phase

+

+ ++

OminusOH∙



119898and 119870









119867)





S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)





+

1sim2nm
















4(bpy)2minus by S

2O8


4(bpy)2minus

and S2O8









2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


OO

O O

OO O

O

OO

OO

O

OO

O

OO

OOO

OO

OO

O

O O

O

O O

O

OO

OO O

O

OO

OO O

O

O

O O O

O

O

OO

OO

O

O O

OOO

O OO

O

OOOO

O O

OO

O

OO

OO O

OO

OO

O OOO

OO

O

O

OO

O

O

O O O O O O OO

OO O O

OO

OO

OO

O OO

OO

O OO

O

OO

O

OO O

OOO

O

OO O

OOOO

OO

OO

O

OOO

OO

O

O O OO

OOO

OO

OO

OOO

OOOO

OO

OO

OOOOO

OOOOO

O

OOO

O O

OOO

OO

O

OOOOO

OO

OOHO

O

OO

HO

OO

OOH O

OO

O OH

OOOHO

O

OO O

OOO

OO

OOO

OO

OO

O O O OO

OO

HO

H2O

H2O

H2O

H2OH2O


Solid

Solid

+

+

+












2particle


2





2) is incorporated









R RR

O2N O2NO2N

N N

OO O

O

minus

O

CC

N

C

O

minus

Ominus

+ CO2


NNNHN NH

OHO

OO P


BrminusH2O

H2O

H2O

H2O

H2O

OHminus

OHminus

OHminus

Stern layer

Bulk phase

+

+ ++

OminusOH∙



119898and 119870









119867)





S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)





+

1sim2nm
















4(bpy)2minus by S

2O8


4(bpy)2minus

and S2O8









2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of











2particle


2





2) is incorporated









R RR

O2N O2NO2N

N N

OO O

O

minus

O

CC

N

C

O

minus

Ominus

+ CO2


NNNHN NH

OHO

OO P


BrminusH2O

H2O

H2O

H2O

H2O

OHminus

OHminus

OHminus

Stern layer

Bulk phase

+

+ ++

OminusOH∙



119898and 119870









119867)





S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)





+

1sim2nm
















4(bpy)2minus by S

2O8


4(bpy)2minus

and S2O8









2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


R RR

O2N O2NO2N

N N

OO O

O

minus

O

CC

N

C

O

minus

Ominus

+ CO2


NNNHN NH

OHO

OO P


BrminusH2O

H2O

H2O

H2O

H2O

OHminus

OHminus

OHminus

Stern layer

Bulk phase

+

+ ++

OminusOH∙



119898and 119870









119867)





S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)





+

1sim2nm
















4(bpy)2minus by S

2O8


4(bpy)2minus

and S2O8









2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


S

S

S

S

S

S

S

SS

O

OO

O

O

OO

O

O OO

OO

O

OO

OO

OOO

OO

O

O

OO

O

O

O

OO

O

O

O

O

Ominus

Ominus

Ominus

OminusOminus

H 3C

H3C

H3 C

H3 CH

3 C

H3 C

H3C

H3C

H3C

H3C

H 3C

H3C

H3CH3C

CH 3

CH3

O

O

OO

OO

O OO

O O

OOO

OO

O

O

O

O

OO

O

OO

O

OS

S

S

S

S

O

O

O

O

OO

O

O

O

O O

O

O

O

OO

O

O

OO

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

Ominus

CH3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3CH3

CH3

CH3

CH3

CH 3

CH3CH

3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH 3CH 3

CH3

H2C

H2C

OH

HC OH

OH

O

O

O

O

O

OH

OH

O

OO

O

O O

O

CH2

CH

CH2 CH2OH

CH2

CH

CH2

CH

CH2

R1

R2 R2

R3 R3

R1

OOO

OO

CH3

333333333

O

OOOOO

AOT(surfactant)

Lipase(biocatalyst)





+

1sim2nm
















4(bpy)2minus by S

2O8


4(bpy)2minus

and S2O8









2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






2831st 00 11075 ln 1198961015840 = minus108472[SDS]

119905+ 470 25522 428 133


119905+ 406 10307 422 149


119905+ 241 2064 238 111

2931st 00 24600 ln 1198961015840 = minus98153[SDS]

119905+ 550 23910 407 129


119905+ 492 9257 388 141


119905+ 341 1678 246 124

3031st 00 51688 ln 1198961015840 = minus73972[SDS]

119905+ 625 18635 375 124


119905+ 587 8836 375 138


119905+ 452 1775 254 128















4 Conclusions
















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of















References













60and polycyclic























6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of















6]4minusrdquo


































5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of












5(4-CNpy)3minus+ S

2O2minus8



4(bpy)2minus + S

2O2minus8








































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 effects of surfactants on the rate of chemical...

Documents