Al-Lohedan, H.A.* and Al-Blewi , F.F.

SURFACTANTS PART 1: OVERVIEW ON THEIR PHYSICAL

PROPERTIES. J. Saudi Chem. Soc., (2008). Vol. 12, No. 4; pp. 489-514.

Department of Chemistry, King Saud University P.O. Box 2455, Riyadh-11451, Saudi Arabia (Received
14th June 2008; Accepted 8th Oct. 2008);

[The book ‘Biological Effects of Surfactants’ was cited in this paper. More info on this book:
http://www.scribd.com/doc/46637373; http://www.scribd.com/doc/46613666; http://www.researchgate.net/profile/Sergei_Ostroumov/blog/7123_FAQ2BookBioeffects;

http://www.researchgate.net/profile/Sergei_Ostroumov/blog/7050_Arabic_on_Detergents ]
Key words: Effects, Surfactants, Detergents, Ecotoxicology, pollution, water quality, environmental studies, environmental chemistry, freshwater, marine ecosystems, aquatic
ecosystems, biotesting, bioassay, synthetic chemicals, pollutants, toxicology, sustainability, water resources; Micelles; Critical micelle concentration, CMC; Micellar shape;
Solubilization, Reversed micelles, Aggregation number, Krafft point, HLB,

Abstract:

‫تﺎﺌ‬.‫تﺎﺒﮐﺮﳌا ﱪﺘﻌﺗًﺎﻴﺤﻄﺳ ﺔﻄﺸﻨﻟاةدﺪﻌﺘﳌا تﺎﻣاﺪﺨﺘﺳﻻا تاذ ﺔﻴﺋﺎﻴﻤﻴﮑﻟا تﺎﺒﮐﺮﳌا ﻦﻣ‬i ‫ﺰﺟ ﺪﻌﺗ ﻲﻬﻓ"أﺔﻴﻠﻴﻔﻴﻔﻣ"ﺚﻴﺣءﺎﻤﻠﻟ ﺐﳏ سأر ﻦﻣ‬
‫نﻮﮑﺘﺗ"ﻲﻠﻴﻓورﺪﻴﻫ"ءﺎﻤﻠﻟ هرﺎﮐ ﻞ‬i‫"ًﺎﻴﺤﻄﺳ ﺔﻄﺸﻨﻟا تﺎﺒﮐﺮﻤﻠﻟ ﺔﺟودﺰﳌا ﺔﻌﻴﺒﻄﻟا هﺬﻫًﻻﺎﺼﺗا ﺎﻬﺘﺒﺴﮐأًﺎ‬.‫ذو"ﰊﻮﻓورﺪﻴﻫ‬i ‫ﻮﻗﳌا ﻞﺜﻣ ﺔﺟﺰﺘﻤﳌا‬
‫ﲑﻏ ﻞﺋاﻮﺴﻟا ﲔﺑﺖ‬i ‫ﺔﻴﺤﻄﺴﻟا تاﺮﺗﻮﺘﻟا ﻦﻣ ﻞﻴﻠﻘﺘﻟا ﻰﻠﻋ ةرﺪﻘﻟا تﺎﺒﮐﺮﳌا هﺬﳍوﺔﺟﺰﺘﻤﳌا ﲑﻏ ﻞﺋاﻮﺴﻟا ﲔﺑ ﻞﺻﺎﻔﻟا ﺢﻄﺴﻟا ﻰﻠﻋ‬.‫ﺰﻟاو ءﺎ‬
‫جاﺰﺘﻣﻻا ﻰﻠﻋ ﺎ ﺪﻋﺎﺴﻣوﺑ ﻰﻤﺴ‬، ‫ﺎﻬﻌﻤﺠﺘﺑ ﻚﻟذو ﺔ ﻴﻨﻴﺒﻟاوﻊﻤﺠﺘﻟا ﻊﻴﻄﺘﺴﺗ ﺎ أ ﺎﻤﮐ‬i ‫ﺎﻣ ﻦ‬i‫ﺔﻴﻧﺎﺑوﺬﻟا ﻦﻣ ﺪ‬، ‫ﺔﮐﺮﳊا ﺔﻴﻠﺑﺎﻗ‬، ‫ﻮﮑﻟﳊا ﺮﻓﻮﺘﻟا‬i‫ﺰ‬i ‫هروﺪﺑ‬
‫اﺬﻫو ﺰﻠﺴ‬i‫ﺎﳌﺎًﺎﻘﺣﻻو يﻮﻴتﺎﺒﮐﺮﻤﻠﻟ يﻮﻴﳊا ﻚﮑﻔﺘﻟاﺔﺒﺋاﺬﻟا ﲑﻏ وأ ﺔﻫرﺎﮑﻟا ﺔ‬i‫ًﺎﻴﺤﻄﺳ ﺔﻄﺸﻨﻟا تﺎﺒﮐﺮﳌا ﻦﻋ ﺔﻤ ﻴﻗ تﺎﻣﻮﻠﻌﻣ مﺪﻘ‬.‫ﻮﻀﻌﻟا‬i
‫ﺔ‬-‫ﺔﻴﻌﺟﺮﳌا ﺔﺎﻟﻘﳌا هﺬﻫ ﻦﻣ لوﻷا ءﺰﳉاﻦﻣﻪﺿاﺮﻌﺘﺳا لﻼﺧ‬i‫و ﺔﻌﻴﺒﻄﻟا ﰲ تﺎﺒﮐﺮﳌا هﺬﻫ ﺪﺟاﻮﺘﺎﻟﻔﻴﻨﺼﺗرﻮﻄﺘﻟا ﻰﻠﻋ ءﻮﻀﻟا ﻲﻘﻠ‬-‫اﺪﺒﻟا ﰲ‬i ‫ﰒ‬
‫ًاﲑﺧأًاﺮﺧآ ﺲﻴﻟوﰲ تﺎﺒﮐﺮﳌا هﺬﳍ ﺔﻴﺋﺎ‬.‫ يﺬﻟارﻮﻄﺗتﺎﺒﮐﺮﳌا هﺬﻫ‬J‫ﻦﻣو ﺔﻣﺎﻌﻟا ﺎﻲﺋﺎﻴﻤﻴﮑﻟاﺐﺣﺎﺻ‬i ‫ﺰﻴﻔﻟا تﺎﻔﺼﻟا ﻢﻫأ ﻞﻴﺼﻔﺘﺎﻟﺑو ءﺰﳉا اﺬﻫ‬
‫ﺶﻗﺎﻨ‬i‫ﻣاﻮﻌﻟا ﻢﻫأ ﻰﻠﻋ ﺪﻴﮐﺄﺘﻟا لﻼﺧ ﻦﻣ ﺔﻴﺋﺎﻨﺜﺘﺳﻻا ﲑ‬i‫ﺎﻌﳌا هﺬﻫ ﺎﻬﺘﺒﺴﮐأ ﱵﻟاو ﻞﻴﺎﻟﶈاتﺎﻔﺼﻟا هﺬﻫ ﻰﻠﻋ ﺮﺛﺆﺗ ﱵﻟا ﻞ‬. Abstract:
Surfactants are among the most versatile chemical compounds. They are amphiphilic molecules
composed of a hydrophilic head and a hydrophobic tail. This dual nature of the surfactants produces a
strong affinity for interfaces between immiscible fluids such as oil and water. Surfactants can reduce
surface and interfacial tensions by accumulating at the interface of immiscible fluids to form micelles
and increase the solubility, mobility, bioavailability and subsequent biodegradation of hydrophobic or
insoluble organic compounds. Part 1 of this review affords valuable information about the surfactants
starting with their natural occurrence and general classification. Then it adds additional light on the
chemistry development of these compounds. Last but not least it discusses in detail the most important
physical properties of these compounds in the solutions, which gave them their extraordinary criteria,
by emphasizing on the factors that affect on these properties. Keywords: Surfactants; Micelles; Critical
micelle concentration CMC; Micellar shape; Solubilization, Reversed micelles, Aggregation number,
Krafft point, HLB.

Contents page 1 Introduction490 2Surfactants490 3Natural surfactants 4914General classifications of

surfactants4925The development of surfactant chemistry4926Physical properties of
surfactants4946.1Micellar formation4946.1.1Normal micellar formation4946.1.2Reversed micellar
formation495* To whom all correspondence should be addressed

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 44906.2Critical micelle
concentration CMC4956.2.1Factors affecting critical micelle concentration CMC4976.2.1.1Hydrocarbon
chain length and structure4976.2.1.2Nature of the polar head group4986.2.1.3The effect of
counterion4996.2.1.4The effect of additives5006.2.1.5The effect of the temperature5006.2.1.6The
effect of pressure5016.3Surfactant and interfacial tension5016.4The Krafft and cloud point5026.5The
HLB concept5026.6Micellar structure and shape5046.7Aggregation number5066.8Solubilization in
aqueous micellar solution508References5091. INTRODUCTIONThe widespread importance of
surfaceactive agents (usually referred to as surfactants)in practical applications, and scientific interest
intheir nature and properties, have precipitated awealth of published literature on the subject [1-31].
Over the past ten years, new surfactantsmolecules have been appearing at a relativelyrapid pace. This
growth in surfactant synthesis hasparalleled the emphasis on increasing the basicperformance of
surfactant formulations and theprovision of new surfactant technology to adiverse range of disciplines.
Although surfactantscience is now a reasonably mature discipline,there is a still room for new molecules
designedfor specific purposes and new applications (suchas nanoparticle synthesis and more diverse
andenvironmentally friendly consumer products).These new materials have spurred on the quest
forimprovedmolecularmodels,computersimulations and improved structure-activityrelationships. New
functionalized surfactantsdepend critically on the nature and placement ofadditional groups. Slight
modifications of themolecular structure with respect to conventionalsurfactants lead to a rich
morphology of structuresthat are being explored by increasingly moresophisticated techniques and , in
turn, enhancingour understanding of their properties at amolecular level [32-36]. This review aims to
provide deeplyknowledge about surfactants, by giving a basicoverview of the nature of surfactants,
theirdevelopment and their physical properties in thesolutions and at interfaces. 2
SurfactantsSurfactants are amphipathic molecules thatconsist of a nonpolar hydrophobic portion,
usuallya straight or branched hydrocarbon orfluorocarbon chain containing 8-18 carbon atoms,which is
attached to a polar or ionic portion(hydrophilic). The hydrophilic portion can,therefore be nonionic, ionic
or zwitterionic, andaccompanied by counter ions in the last two cases[37]. These compounds are termed
surfactants,amphiphiles, surface-active agents, tensides, or, inthe very old literature, paraffin-chain
salts. Themost commonly used term, surfactant, wasoriginally registered as a trademark for
selectedsurface-active products and later released to thepublic domain [38]. The adsorption of
thesesurfactants at gas/liquid and liquid/liquid interfacehas long been recognized as key factor in
widevariety of practical applications areas which areillustrated in terms of mineral and
petroleumprocessing, biological systems, pharmaceuticals,health, personal care products, foods and
cropsproduction. Owing To their tendency to beadsorbed at interface, they are often called assurface
active agents or colloidal surfactants. Theyundergo self-association resulting in colloidalaggregates of
high molecular weight calledmicelle [39]. The aggregates generally contain atleast 50 monomers when
the surfactant is ionic,but they are usually much higher, when it isnonionic [40,41].

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No. 4491The
unusual properties of aqueous surfactantsolutions can be ascribed to the presence of ahydrophilic group
and a hydrophobic chain (ortail) in the molecule. The hydrocarbon chaininteracts weakly with water
molecules in anaqueous environment, whereas. The polar or ionichead group usually interacts strongly
with anaqueous environment, in which case it is solvatedvia dipole-dipole or ion-dipole interactions
[42].3 Natural SurfactantsIt is not exaggeration to say that the life aswe know it would not be possible
withoutsurfactants. Naturally occurring surfactants play aliterally vital role in living organisms. They
areable to perform these roles only because they canself-aggregate into species, namely
micelles,bilayers and liquid crystals. Cell membranescomposed mainly of amphiphiles, which are self-
assembled into a bilayer structure with themolecules oriented so that the hydrophilic groupsare on the
outside of the membrane and thehydrophobic groups avoid contact with theaqueous regions by being
packed closely togetherinside the membrane. In mammalian cells, theprimary amphiphiles are
phospholipids, which arederivatives of glycerol esters with long-chain fattyacids, Table 1 [43]. In milk,
the fat is mainly in the form oftriglycerides but a small amount is present asphospholipids and
diglycerides, which aresurfactants that help to stabilize the emulsion inwater. During digestion fats are
converted intomore soluble species, which can be transportedaround the body more readily. A variety
ofsurfactants are involved at different stages duringthis digestive process. Bile salts are surfactants
produced in theliver and stored in the gall-bladder. A typicalexample is sodium glycocholate whose
structureis shown in Table 1. In the blood stream the fattyacids leave these surfactant complexes to
combinewith proteins such as serum albumin to formlipoproteins, which self-organize into
speciessuitable for transport to various destinationsaround the body [43].Table 1: Examples of naturally
occurring surfactants*TypeStructureOccurrencePhospholipidsR CO O CH2CHCH2O P O XO-OOCORX = HX
= CH2CH2 NH3+X = CH2 CH2 N+(CH3)3Cell membraneFatty acidsR–CO–OHSebum IntestinesBile
saltsNHCH2COO-Na+OHHOOHOSodium glycocholateGall-bladderIntestines*R represents mixtures of
saturated and unsaturated linear alkyl groups with chain lengths in range C10-C20.

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 44924 General
Classifications of SurfactantsA simple classification of surfactants basedon the nature of the hydrophilic
group iscommonly used. The main classes may be distin-guished, namely anionic, cationic, nonionic
andamphoteric, Table 2 gives some examples ontheses classes [42]. A useful reference isMcCutcheon
[44], which is produced annually toupdate the list of available surfactants. Van Os etal. have listed the
physicochemical properties ofselected anionic, cationic and nonionic surfactants[45]. In addition,
another class of surfactants,usually referred to as polymeric surfactants, haslong been used for the
preparation of emulsionsand suspensions and their stabilization [37].Fluorocarbon and silicone
surfactantsrepresent a special class of surfactants [46,47].These surfactants can lower the surface
tension ofwater to below 20 mN m-1 (most surfactants lowerthe surface tension of water to values
above 20mN m-1). Fluorocarbon and silicone surfactantsare sometimes referred to as superwetters as
theycause enhanced wetting and spreading of theiraqueous solution. However, they much
moreexpensive than conventional surfactants and areonly applied for specific applications whereby
thelow surface tension is a desirable property [37].Biosurfactants are surface active
compoundsproduced by microorganisms. Most microbialsurfactants are complex molecules,
comprisingdifferent structures that include lipopeptides,glycolipids, polysaccharide-protein complex,
fattyacids and phospholipids. Biosurfactants arebecoming important biotechnology products
forindustrial and medical applications due to theirspecific modes of action, low toxicity, relativeease of
preparation and widespread applicability.Although biosurfactants exhibit such importantadvantages,
they have not been yet employedextensively in industry because of relatively highproduction costs
[48].5 The Development of Surfactant ChemistryDespite the significant use of surfactants inmany
industries, it is somewhat surprising that thebulk of surfactant applications have been, untilvery
recently, the domain of single-headed, singletailed surfactants. Performance limitations ofconventional
sulphate and sulphonate surfactants,related to their hard water tolerance or their coldwater solubility,
initiated some early interest inalternate surfactant structures. In the mid-1950s,Evans began
investigating sulphate surfactants inwhich the point of substitution of the sulphatesurfactants was
varied and the micellar propertieswere correlated to the point of the substitution ofsulphate group
[49].This was one of the earliest examples of theestablishment of a structure-performance relation-ship
in family of surfactants. Stirton et al. outlinedthe synthesis of one of the first 'tunable'surfactants, the
disodium α- sulphocarboxylates.These surfactants were found to have excellentproperties in terms of
hard water tolerance, foamstability and detergency when compared to theirsingle headed counterparts
[50, 51]. They sufferedfrom the drawback that they are irritating to theskin, a problem that is faced with
most highcritical micelle concentration CMC surfactants[52].Interest in developing new amphilphiles
usedas detergent formulators found they could enhancethe performance of their commercial products
bythe judicious selection of additives. By the early1980s however, interest in surfactants derivedfrom
non-linear alkylbenzene sources began toincreases as it become clear that consumerdemand for "newer
and better'' detergents wasoutpacing the ability of detergent manufacturers toreformulate their
products when the maincomponent was still the conventional single-head,single-tail amphiphile. Hence
the synthesis ofnovel surfactants has emerged as a viable andimportant topic in the literature. In
modernsurfactant papers it is not unusual to observe theinvestigation of the properties of vitamin E-
basedsurfactants [53], sugar-based surfactants [54] andmany others [55].One of the most exciting
developments inthe field of surfactant chemistry is the emergenceof the Gemini surfactants in the late
1980s andearly of the 1990s. The term Gemini surfactant,coined by Menger, has become accepted in
thesurfactant literature for describing the dimericsurfactants, surfactants molecules that have
twohydrophililc (chiefly ionic) groups and two tailsper surfactants molecules [56,57]. These twinparts of
the surfactants are linked by a spacergroup of varying length (most commonly amethylene spacer or an
oxyethylene spacer).

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No. 4493Table 2:
Classifications of surfactants.ClassExamplesStructuresAnionicNa stearateCH3(CH2)16COO- Na+Na
dodecyl sulphateCH3(CH2)11SO4- Na+Na dodecyl benzene sulphonateCH3(CH2)11C6H4SO3-
Na+Sodium cholateOHHOOHCOO-Na+Cationic1-Dodecyl pyridinium halideCH3(CH2)11N+ C5H5X-, (X=
Cl-, Br-, I-)Dodecyltrimethylammonium halideCH3(CH2)11N+ (CH3)3X-, (X= Cl-,
Br-)Tetradecyltrimethylammonium halideCH3(CH2)13N+ (CH3)3X-Cetyltrimethyammoinium
halideCH3(CH2)15N+ (CH3)3X-NonionicPolyoxyethlene alcoholCnH2n+1(OCH2CH2)mOHAlkylphenol
ethoxylateC9H19-C6H4-(OCH2CH2)nOHPolysorbate
80O(C2H4)xOHCH(OC2H4)yOHCH2(OC2H4)zRHO(C2H4O)ww+x+y+z = 20R= (C17H33)COOn-
OctylsulfinylethanolCH3(CH2)7SOCH2CH2OHZwitterionic Dodecyl betaineC12H25N+ (CH3)2CH2COO-3-
(Dodecylmethylammonio)propane-1-SulfonateCH3(CH2)11N+ H(CH3)CH2CH2CH2SO3-N-
Dodecylaminobenzylphosphinic acidCH3(CH2)11N+ H2CH(C6H5CH2) PO2-H

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 4494A number of reviews
cover the properties ofcationic and anionic surfactants [58-60]. Geminisurfactants possess a number of
superiorproperties when compared to conventional single-head, single tailed surfactants. The Geminis
tendto exhibit lower CMC values, increase surfaceactivity and lower surface tension at the CMC,enhance
solution properties such as hard-watertolerance, superior wetting times and lower Krafftpoints. Given
these performance advantages ofGemini surfactants one can anticipate their use ina myriad of
surfactant applications (e.g., soilremediation, oil recovery and commercialdetergents), given a favorable
cost/performanceratio [61].6 Physical Properties of Surfactants 6.1 Micelle Formation6.1.1 Normal
Micelle FormationThe physical properties of surfactants differfrom those of smaller or
nonamphipathicmolecules in one major aspect, namely the abruptchanges in their properties above a
criticalconcentration. Figure 1 illustrates with plots ofseveral physical properties (osmotic
pressure,turbidity, solubilization, magnetic resonance,surface tension, equivalent conductivity and self-
diffusion) as a function of concentration for anionic surfactant [37]. In aqueous solution dilute
concentrations ofsurfactant act much as normal electrolytes, but athigher concentrations very different
behaviorresults. This behavior is explained in terms of theformation of organized aggregates of
largenumbers of molecules called micelles, in whichthe lipophilic parts of the surfactants associate inthe
interior of the aggregate leaving thehydrophilic parts to face the aqueous medium,Figure 2 [37,42]. The
formation of micelles inaqueous solution is generally viewed as acompromised between the tendency
for alkylchains to avoid energetically unfavorable contactwith water, and desire for the polar parts
tomaintain contact with the aqueous environment.This effect is known as hydrophobic effect [42].Figure
1: Schematic representation of the concentration dependence of somephysical properties for solutions
of a micelle-forming surfactant.

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No. 4495Figure 2:
An illustration of a spherical micelle (for dodecylsulphate) emphasizing the liquid-like character with
adisordered hydrocarbon core and a rough surface. Due to the presence of the hydrophobiceffect,
surfactant molecules adsorb at interfaces,even at low surfactant concentrations. As therewill be a
balance between adsorption anddesorption, the interfacial condition require sometime to establish. The
surface activity ofsurfactants should therefore be considered adynamic phenomenon. This can be
determined bymeasuring surface or interfacial tensions versustime for a freshly formed surface. At a
specific,higher, surfactant concentration, known as thecritical micelle concentration (CMC),
molecularaggregates termed micelles are formed. The CMCis a property of the surfactant and a number
ofother factors including the temperature, pressure,and the presence and nature of additives,
sincemicellization is opposed by thermal andelectrostatic forces [42].6.1.2 Reversed Micelle
FormationAggregates can also occur in nonpolarsolvents. These systems are called reversemicelles or
inverted micelles as seen in Figure 3[62]. Head groups of surfactant monomers arelocated inside to form
a polar core andhydrocarbon tails are projected toward the bulksolution to form the outside shell of the
micelle. Ifthere is any water in the solution, it will beentrapped in the core. Reverse micelles are able
tosolubilize a relatively large amount of water intheir cores and this capacity can allow them tosolubilize
water-soluble substances in nonpolarsolvent. For example, it has been reported thatwater can be
solubilized in carbon dioxide,nonpolar solvent, when the appropriate surfactantis chosen [63]. 6.2
Critical Micelle Concentration (CMC)The critical micelle concentration CMCindicates the usually narrow
range ofconcentrations separating the limits below whichmost of the surfactant is in monomeric state
andabove which virtually all additional surfactantsenter the micellar state [64]. For
surfactantscontaining long chain alkyl group, the CMC isusually between 10-4 and 10-2 M. A list of
theCMC values of some selected surfactants at 25°Cis given in Table 3 [65]. The sharpness of thebreak in
the physical properties depends on thenature of micelle and on the method of CMCdetermination.
Markerjee and Mysels reviewedabout 70 methods which have been published forCMC determination
[66]. There are, however,great differences in the sensitivity and reliabilityamong different methods
[67,68]. Most hightemperature and pressure.

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 4496Figure 3: Formation of
reverse micelle.Table 3: Micellar parameters of some selected surfactants at 25°C.SurfactantCMC
(M)Aggregation number (N)Decylammonium bromide5.0 ×10-31100Decyltrimethylammonium
bromide6.50 ×10-248Dodecylammonium chloride1.50 ×10-255.5Dodecyltrimethylammoium
bromide1.50 ×10-250Dodecylpyridinium bromide1.10 ×10-286Tetradecyltrimethylammonium
bromide3.50 ×10-375Hexadecyltrimethylammoium bromide9.20 ×10-461Hexadecylpyridinium
chloride9.0 ×10-495 (in 0.0175M NaCl)Sodium decylsulphate3.30 ×10-250Sodium dodecanoate2.40 ×10-
256 (in 0.013M KBr)Lithium dodecylsulphate8.80 ×10-363Sodium dodecylsulphate8.10 ×10-362Sodium
dodecylsulphonate9.80 ×10-354Sodium tetradecylsulphate2.10 ×10-3138 (in 0.01M
NaCl)Polyoxyethylene(6)octanol9.90 ×10-332Polyoxyethylene(6)decanol9.0 ×10-
473Polyoxyethylene(6)dodecanol8.70 ×10-5400Polyoxyethylene(23)dodecanol(Brij35)(6.0-9.1 ×10-
540CMC studies have been by conductivity,calorimetry, or NMR, and have been limited toionic
surfactants [69-75]. Conductometrictechniques are unsuitable for nonionic orzwitterionic surfactants, or
for the backgroundelectrolyte concentrations are significant. In suchcases specialized surface tension
[76,77] ordynamic foam stability measurements have beenemployed [78]. The CMC values are
important in virtuallyall of the process industry surfactant applications,from mineral processing to
formulation ofpersonal care products and foods, to drug deliverysystems, and to new surfactant
remediationtechnologies. In these processes, surfactant mustusually be present at a concentration
higher thanthe CMC because the greatest effect of thesurfactant, whether in interfacial tension
lowering[79], emulsification, suspension stabilization, as adelivery vehicle, or promoting foam stability,
isachieved when a significant concentration ofmicelles is present. The CMC is also of interestbecause at
concentration above this value theadsorption of surfactant at interfaces usually

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No. 4497increases
very little. That is, the CMC frequentlyrepresents the solution concentration of surfactantfrom which
nearly maximum adsorption occurs[42].6.2.1 Factors Affecting Critical MicelleConcentration CMC6.2.1.1
Hydrocarbon Chain Length and Structure: For the same head group, compoundscontaining longer
hydrocarbon chains formmicelles at lower concentrations (decrease ofCMC) than those containing short
chains. Thedecrease of interfacial free energy onmicellization is more for longer chains than forshort
ones, and it is possible that there is morewater structure loss from transfer of a long chaininto a micelle
than a short one. Both of thesefactors promote micellization [80]. The CMC is related to the number of
carbonatoms (n) in a straight hydrocarbon chain byEquation. (1): Log CMC = A – Bn(1)Where A and B are
constants for homologousseries [81]. Table 4 lists some values of A and Bdetermined from experimental
data. Figure 4shows a linear relationship between log CMC andthe number of carbon in chain length. For
chainsof greater than 16 carbon atoms this relationshipno longer holds and further increase in
chainlength often has no appreciable effect on theCMC, possibly due to the coiling of the longchains in
solution. In case of branchedhydrocarbon chains, the effect on the CMC (withincrease in number of
carbon atoms) is not largerthan in a straight chain [82]. Table 4: The values of A and B constants in the
relationship log CMC = A - BnBATemperature(°C)Surfactants0.301.8520Na carboxylates0.291.9225K
carboxylates0.301.5125Na (K) n-alkyl-1-sulphates or -sulphonates0.291.5940Na n-alkyl -1-
sulphonates0.261.1555Na n-alkyl -1- sulphonates0.281.4260Na n-alkyl -1- sulphonates0.301.4245Na n-
alkyl -1- sulphates0.281.3560Na n-alkyl -1- sulphates0.271.2855Na n-alkyl -2- sulphates0.291.6855Na p-
n-alkylbenzene sulphonates0.271.3370Na p-n-alkylbenzene sulphonates0.271.2525n-alkylammonium
chlorides0.301.7945n-alkylammonium chlorides0.301.7725n-alkyltrimethylammonium
bromides0.291.7760n-alkyltrimethylammonium bromides0.331.2325n-alkyltrimethylammonium
chlorides (in 0.1M NaCl)0.311.7230n-alkylpyridinium bromides0.491.8225n-CnH2n+1(OC2H4)6OH

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 4498Figure 4: Variation of
critical micelle concentration CMC with hydrocarbon chain lengthfor: (a) Sodium alkyl sulphate and
alkyltrimethylammonium bromides. (b) Hexaoxyethylene monoalkyl ethers6.2.1.2 Nature of The Polar
Head Group:The CMC of nonionic surfactants are muchlower than those of ionic ones for the
samehydrocarbon chain lengths, due to the lack ofelectrical work in transferring a monomer into
amicelle for the nonionic. For a given alkyl chainof surfactant, CMC's increase in the ordernonionic
(polyoxyethylene glycol monoether) <zwitterionic < ionic (cationic or anionic) as shownin Table 5 [80].
The number of ionic groups also affects theCMC, Table 6. The more ionized groups presentin surfactant,
the higher the CMC, due to theelectrical work to form the micelles as the numberof groups increases.In
nonionic surfactants, increase of thepolyoxyethylene chain causes an increase in theCMC as illustrated
in Table 7. Increasing thepolyoxyethylene chain length makes the monomermore hydrophilic giving
higher CMC [80]. The position of the head group in thehydrocarbon chain also affects the CMC.
Thecloser the head group to the center of chain, thehigher the CMC; due to the two branches of
thechain partially shielding one another, Table 8. Theinterfacial energy are smallest when the –
SO4Nagroup is present at position 7, hence there is lessenergy, saving on micellization for this
compoundthan when the head group is present in position 1[80].

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No. 4499Table 5:
CMC's for various surfactants in water at temperatures between 20° and 30°C.103 CMC,
(M)Compound8.1CH3(CH2)11SO4Na14.4CH3(CH2)11N(CH3)3Br12.5CH3(CH2)11COOK10.0CH3(CH2)11S
O3Na14.0CH3(CH2)11NH3Cl16.0CH3(CH2)11NC5H5Br0.21CH3(CH2)11N(CH3)2O0.087CH3(CH2)11(OCH
2CH2)6OHTable 6: The effect of the number of ionic groups on the CMC.103 CMC
(M)Compound12.5CH3(CH2)11COOK130.0CH3(CH2)9CH(COOK)2280.0CH3(CH2)7CH(COOK)
CH(COOK)2Table 7: The effect of the number of polyoxyethylene on the CMC of
hexadecylpolyoxyethyleneethers CH3(CH2)15(OCH2CH2)xOH.X6791215106CMC
(M)1.701.702.102.303.0Table 8: The effect of position of polar head group in the hydrocarbon chain on
the CMC.R1CHSO4NaR2Position of –SO4Na123457103 CMC (M)2.403.304.305.156.759.70For the similar
reasons the presence of adouble bond in a chain causes an increase inCMC, e.g. for potassium stearate
at 55°C theCMC = 4.5 ×10-4M, while for potassium oleate at50°C it is 1.2 ×10-3M [80].6.2.1.3 The Effect
of Counterion:A number of studies indicate counterionassociated with an ionic group have
pronouncedeffect on miceller properties [83-87]. Mukerjee etal concluded for alkali metal ions that
thehydrated ion interacts with the micelle and thatsmaller hydrated ions have a greater interactionwith
the micellar surface leading to a lower degreeof counterion dissociation and a more compactdouble
layer [84]. The nature of the counterionhas some effect on the CMC as shown in Table9.CMC's were
lowest for the least-solvatedcounterions [80].The valence of counterion is significant.While simple
monovalent inorganic counterionsgive roughly the same CMC, increasing thevalence to 2 give a
reduction of the CMC byroughly a factor of 4. Organic counterions reducethe CMC compared to
inorganic ones, the more sothe larger the nonpolar part [81].

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 4500Table 9: The effect of
counterion on the CMC of CH3(CH2)11SO4X at 25°C.XLiNaK*Cs*N(CH3)4103
CMC(M)8.808.107.806.905.50*Measurements at 40°C.6.2.1.4 The Effect of Additives:The effects of
added substances on the CMCare complicated and depend greatly on whetherthe additive is solubilized
in the micelle, or in theintermicellar solution. Many studies have beenmade on the effect of salts on the
CMC of ionicsurfactants [88-92]. The addition of electrolytelike salts decreased the CMC of ionic
micelles. InTable 10 the results for sodium dodecyl sulphateSDS and cetylpyridinium chloride with
sodiumchloride are given. This decrease has beenattributed to the screening action of the
simpleelectrolytes which lowers the repulsive forcesbetween the polar head groups and hence
lesselectrical work is required in micelle formation[80]. For nonionic micelles, electrolyte additionhas
little effect on CMC values [93]. When nonelectrolytes are added to micellarsolution, the effects are
dependent on nature ofadditive. The effect of added alcohols have beenreported for nonionic system,
where methanol andethanol cause an increase in CMC and higheralcohol butanol and pentanol cause a
decrease inCMC [94]. The CMC increasing effect has beenexplained to weakening of the
hydrophobicbonding. The CMC decreasing effects werethought to be a consequence of the penetration
ofthe alcohols into the palisade layer of the micelle,forming a mixed micelle.Kodama and co-workers
have studied theeffects on the CMC of aqueous solutions ofsodium and lithium dodecyl sulphates [95].
TheCMC was reported to be increased in the presenceof urea. They discussed the result in terms of
thebreaking effect of urea on the water structurearound the hydrocarbon chains as well as
thecounterions of the surfactants which resultreducing the driving forces for micellization. Nonpolar
additives tend to have little effecton the CMC [42].6.2.1.5 The Effect of Temperature: The CMC would at
first sight be expected toincrease as temperature increases, due to a
thermalagitationdecreasingadhesionbetweenmonomeric, so shifting the equilibrium to favorthe
monomeric species. This is probably true forionic surfactants at higher temperature. At
lowertemperature (generally at 30°C or below) theCMC decreases with increasing temperature,probably
due to desolvation of parts of monomerwhich make it more hydrophopic, Figure 5. For the nonionic
surfactants the CMCdecreases with increasing temperature up to thehighest value measured, indicating
thatdesolvation effects on both hydrocarbon andpolyoxyethylene chains of monomer may be solarge
that they outweigh possible effects ofthermal agitation in breaking up the micelles, Figure 5
[80].Table10: The effect of electrolyte on the CMC of:a) Sodium dodecyl sulphate b) Cetylpyridinium
chloride. a)Sodium dodecyl sulphate[NaCl],(M)0.000.030.200.50103 CMC,(M)8.103.100.900.52b)
Cetylpyridinium chloride[NaCl],(M)0.01750.05840.4380.730103 CMC,(M)1.200.870.480.41

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No. 4501Figure 5:
Variation of CMC with temperature for: (a) sodiumdodecyl sulphate (b) CH3(CH2)9(OCH2CH2)5OH
6.2.1.6 The Effect of Pressure:The effect of pressure on series ofalkyltrimethylammonium bromides and
onsodium dodecyl sulphate SDS has been studied[80]. The CMC increases up to pressures of about1000
atmospheres and decreases with furtherincreases of pressure. It has been suggested thatthe surfactant
molecules when present in themicelle are in a more expanded condition thanwhen present as the
monomer in solution, so thatthe initial effects of pressure tend to compress themicelle and militate
against the increased freedomof the monomer in the micelle, thus giving a risein CMC.The decrease in
CMC on increasing thepressure above 1000 atmospheres may be due toan increase in dielectric
constant of water, makingless electric work necessary to bring a monomerinto a micelle.6.3 Surface and
Interfacial Tension When surfactants concentrate in an adsorbedmonolayer at a surface or interface the
physicalproperties of the interface can be very importantin all types of natural phenomena and
industrialprocessing operations.When surfactant molecules adsorb at aninterface they provide an
expanding force andcause the interfacial tension to decrease (at leastup to the CMC) [96]. If the
interface thenundergoes sudden expansion a surface tensiongradient is established which induces liquid
flowin the near-surface region, termed the Marangonieffect [97].

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 45026.4 The Krafft and
Cloud PointsThe solubilities of micelle-forming show astrong increase above a certain temperature,
atermed the Krafft point as illustrated in Figure 6.Below the Krafft point the solubility of thesurfactant is
too low for micellization so solubilityalone determines the surfactant monomerconcentration. Above
the Krafft point a relativelylarge amount of surfactant can be dispersed inmicelles and solubility
increases greatly. AboveKrafft point maximum reduction in surface orinterfacial tension occurs at the
CMC because theCMC then determines the surfactant monomerconcentration [98].Nonionic surfactants
do not exhibit Krafftpoints; their solubility decreases with increasingtemperature and these surfactants
may begin tolose their surface active properties above thetransition temperature referred to as the
cloudpoint. This occurs because above the cloud point asurfactant rich phase of swollen
micellesseparates; the transition is visible as a markedincrease in dispersion turbidity. The addition
ofionic surfactants increases the cloud points of theirnonionic counterparts. Recent studies suggest
thatan increase in cloud point can be attributed tosurface charge of the micelle; therefore
increasingelectrostaticrepulsionreducesmicellecoalescence responsible for clouding [99].Figure 6:
Surfactant solubilities and Krafft point. 6.5 The HLB ConceptA rule of thumb in emulsion technology
isthat water-soluble emulsifiers tend to give O/Wemulsions and oil-soluble emulsifiers W/Oemulsions.
This concept is known as Bancroft'srule [81].Bancroft's rule is entirely qualitative. In anattempt to extend
this rule into some kind ofquantitative relationship between surfactant andhydrophilicity and function in
solution, Griffinintroduced the concept of hydrophilic-lipophilicbalance (HLB) of surfactant [100]. The
HLBnumbers for normal nonionic surfactants wasdetermined as follow: For alcohol ethoxylates and
alkylphenolethoxylates: HLB = wt % ethylene oxide / 5 (2)The HLB number concept has proved usefulin
the first selection of a surfactant for a givenapplication. Table 11 shows how the appearance

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No. 4503of
aqueous surfactant solutions depends on thesurfactant HLB. It also indicates some typicalapplications of
surfactants with different HLBnumber intervals. Griffin's number concept was later extendedby Davies,
who introduced a scheme to assignHLB group number to chemical groups whichcompose a surfactant,
Equation (3). HLB = 7 + Σ ( hydrophilic group numbers)+ Σ(lipophilic group numbers) (3 )Some typical
group numbers are shown inTable 12. Form this table it can be seen thatsulphate is a much more potent
polar group thancarboxylate and that terminal hydroxyl group in apolyoxyethylene chain is more
powerful in termsof hydrophilicity than a sugar hydroxyl group.Factors such as electrolyte concentration
inwater, oil polarity and water to oil ratio may alsoinfluence which type of emulsion forms.Evidently, the
HLB number cannot be used as auniversal tool to select the appropriate emulsifieror to determine which
type of emulsion will formwith a specific surfactant [81].The HLB is an indicator of
emulsifyingcharacteristics of an emulsifier but not itsefficiency. Thus, while all emulsifiers having
highHLB tend to promote O/W emulsions, there willbe a considerable variation in the efficiency
withwhich those emulsifiers act for any given system. Just as solubilities of emulsifying agentsvary with
temperature so does the HLB, especiallyfor the nonionic surfactants. A surfactant may thusstabilize O/W
emulsions at low temperature, butW/O emulsions at some higher temperature. Thetransition
temperature, at which the surfactantchanges from stabilizing O/W to W/O emulsions,is known as the
phase inversion temperature, PIT.At the PIT, the hydrophilic and the oleophilicnatures of the surfactant
are essentially the same[101].Table 11: Use of Griffin's HLB number concept.Appearance of aqueous
solutionHLB number rangeNo dispersibility1-4Poor dispersibility3-6Milky dispersion after agitation6-
8Stable milky dispersion8-10Form translucent to clear10-13Clear solution13-20ApplicationHLB number
rangew/o Emusifier3-6Wetting agent7-9o/w Emulsifier8-14Detergent9-13Solubilizer10-13Dispersant12-
17

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 4504Table 12: HLB
numbers for hydrophilic and lipophilic groups.HLB numberGroupHydrophilic35.7-SO4Na21.1-CO2K19.1-
CO2Na9.4-N (tertiary amine)6.3Ester (sorbitan ring)2.4Ester (free)2.1-CO2H1.9-OH (free)1.3-O-0.5-OH
(sorbitan ring)Lipophilic-0.870-CF3-0.870-CF2--0.475-CH3-0.475-CH2--0.475-CH-6.6 Micellar Structure
and Shape The shape of the micelle produced inaqueous media is of important in determination
ofseveral physical properties of the surfactantsolution, such as its viscosity, its capacity tosolubilize
water-insoluble material, and its cloudpoint. At the present time, the major types ofmicelles can be
summarized in Figure 7 [81]. (a) Relatively small, spherical structures(aggregation number > 100). (b)
Elongated cylindrical, rod-like micelles withhemispherical ends (prolate ellipsoids). (c) Flat lamellar
micelles (disk-like extendedoblate spheroids).(d) Reversed or inverted micelles which have awater core
surrounded by the surfactant polarhead group.(e) A bicontinuous structure with the
surfactantmolecules aggregated into connected filmscharacterized by two curvatures of oppositesign. (f)
Vesicles, more or less spherical structuresconsisting of lamellar micelles arranged inone or more
concentric spheres. In aqueous media, the surfactant moleculesare oriented, in all these structures, with
theirpolar heads toward the aqueous phase and theirhydrophobic groups away from it. In ionicmicelles,
the aqueous solution-micelle interfacialregion contains the ionic head groups, the Sternlayer of the
electrical double layer pertaining tothese groups; somewhat more than one-half of thecounterions
associated with the micelle, andwater, the remaining counterions are contained inthe Gouy-Chapman
portion of the double layerthat extends further into the aqueous phase, Figure8. For nonionic micelles,
like polyoxyethylenated,the structure is essentially the same, except thatthe outer region contains no
counterions, butincludes coils of hydrated polyoxyethylene chains.

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No. 4505Figure 7:
The different structures of surfactant.Figure 8: A two-dimensional schematic representation ofthe
regions of a spherical ionic micelle.

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 4506The interior region of
micelle, containing thehydrophobic groups, is of radius approximatelyequal to the length of the fully
extendedhydrophobic chain. The aqueous phase is believedto penetrate into the micelle beyond
thehydrophobic head groups, and the first fewmethylene groups of hydrophobic chain adjacentto the
hydrophobic head are often considered inthe hydration sphere. It is therefore useful todivide the
interior region into an outer core thatmay be penetrated by water and an inner corefrom which water is
excluded [15]. In nonpolar media, the structure of themicelle is similar but reversed, with thehydrophilic
heads comprising the interior regionsurrounded by an outer region containing thehydrophobic groups
and nonpolar solvent. Dipole-dipole interactions hold the hydrophilic headstogether in the core.
Changes in temperature,concentration of surfactant, additives in the liquidphase, and structural groups
in the surfactant mayall cause change in the size, shape, andaggregation number of the micelle, with
thestructure varying from spherical through rod- ordisk-like to lamellar in shape [15, 102].A theory of
micellar structure based upon thegeometry of various micellar shapes and the spaceoccupied by the
hydrophilic and hydrophobicgroups of the surfactant molecules, has beendeveloped by Israelachvili
[103]. The volume VHoccupied by the hydrophobic groups in the micellecore, the length of hydrophobic
group in the corelc, and the cross-sectional area aο occupied by thehydrophilic group at micelle-solution
interface areused to calculate a dimensionless value known asthe critical packing parameter (CCP),
Equation(4).CCP = VH / lc aο(4)From Tranford [104], VH = 27.4 + 26.9n A°,where n is the number of
carbon atoms of chainembedded in the micellar core (the total numberof carbon atoms in the chain, or
one less); lc ≤ 1.5+ 1.265n A°, depending upon the extension of thechain. For saturated, straight chains,
lc may be80% of the fully extended chain. Analysis of thedifferent geometrical shapes of surfactants
leadsto the simple rules illustrated in Figure 9 [15].Considering what surfactants fall into thedifferent
categories of Figure 8, spherical micelles(CCP< 1/3) are found for single-chain surfactantswith strongly
polar head group, like an ionic headin the absence of an electrolyte, and also fornonionic surfactants
with large head groups. Therange of CCP values of 1/3 – 1/2 and rod-likestructures are characteristic of
single-chain ionicswith an added electrolyte, single-chain ionics witha strongly bound counterion or
nonionic with anintermediate head group size. Higher CCP valuesare characteristic of double–chain
amphiphiles ornonionic with small head groups [81].6.7 Aggregation NumberThe aggregation number
(N), the number ofmonomers, determines the size and geometry ofthe micelle and hence is an
important quantity.Aggregation numbers for surfactants in aqueoussolution generally range between 10
and 100.Available methods for determining the number ofmonomers in the micelle include light
scattering,diffusion, viscosity and sedimentation velocity,ultrafiltration, and nuclear magnetic
resonanceNMR [15]. Some aggregation numbers ofsurfactants are listed in Table 3. From geometric
considerations, the aggre-gation numbers (N) of micelles in aqueous mediashould increase rapidly with
increase in length ofthe hydrophobic group lc of surfactant molecule,and decrease with increase in the
cross-sectionalarea of hydrophilic group aο or the volume of thehydrophobic group VH [15].Ionic
surfactants that containing a singlelong alkyl chain and zwitterionics in which theelectrical charges are
not on adjacent atoms showaggregation numbers of less than 100 in aqueoussolutions containing low or
moderate concen-trations of NaCl (≤ 0.1M). This is indicative ofspherical micelle formation. At high salt
content,however, N increases sharply with surfactantconcentration, with formation of rod likecylindrical
or disk-like lamellar micelles. Ionic surfactants having two long (≥ 6carbons) alkyl chains have high VH
values relativeto lc and probably do not form spherical micelles.They have values of N that increase
withsurfactant concentration, the increase becomingpronounced with increase in the length of
thechains. Some of these micellar solutions are in

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No.
4507equilibrium with lamellar liquid-crystal structures[15]. Furthermore, the addition of
neutralelectrolyte to solutions of ionic surfactants inaqueous solution causes an increase in
theaggregation number, presumably because ofcompression of the electrical double layersurrounding
the ionic heads. The resultingreduction of their mutual repulsion in the micellepermits closer packing of
the head groups (aο isreduced), with consequent increase in N.Meanwhile, the effect of neutral
electrolyteon the aggregation number of micelles of nonionicsurfactants in aqueous solution is
somewhatunclear, with both increases and decreases beingobserved on addition of electrolyte. In either
case,however, the effect appears to be small.As a final point, an increase in thetemperature appears to
cause a small decrease inthe aggregation number in aqueous medium ofionic surfactants, presumably
aο is increased dueto thermal agitation. For nonionic surfactants thereis a very large increase in N when
the temperatureapproaches the neighborhood of the ''cloud point''[15].Figure 9: Critical packing
parameters (CCPs) of Surfactant molecules andpreferred geometrical structures.

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J. Saudi Chem. Soc., Vol. 12, No. 4; pp. 489-514 (2008) 4896.8 Solubilization in Aqueous Micellar
SolutionThe process of solubilization involves thetransfer of cosolute (usually referred to as thesubstrate
or solubilizate) from the pure state,either crystalline solid or liquid to micelles [105].The cosolute can be
either polar or nonpolar. Thesolubility however, increases when the CMC ofthe surfactant is reached,
but above the CMC theincrease in solubility of the substrate is directlyproportional to the wide range of
surfactantconcentration [39]. This increase of solubility ofthe solute in micellar medium is due to
thesolubilization of the substrate molecules into themicelles. According to Menger's model of
micellarstructure three environments for the solubilizatescan be considered: the micelle core, the
hydratemicellar grooves and the bulk aqueous phase[106]. A thermodynamic treatment has
beendeveloped to determine the origin of the selectivesolubilization, which predicts the
molarsolubilization ratios of various compounds bothsingly and in mixtures [107]. This treatment
takesinto account the following observations:- (1) the change in the surface area per amphiphileof the
micelle due to the incorporation of thesolubilizates ( this causes a change in the stericand electrostatic
interactions between the headgroups and in the micellar core-water interaction). (2) the hydrophobic
effect associated with thetransfer of the solubilizates from water to themicelle. (3) the entropy of mixing
of surfactants andsolubilizates in the micelle. The relative balance between the changes inthe head
groups principally determines the natureand the magnitude of solubilization.In Fact, several factors
affect solubilzationincluding the structure of surfactant, solubilizate,additives and temperature [105].
For solubilizateswhich are located either in the micelle core or in aposition of deep penetration within
the micelle,solubilization could be expected to increase in thealkyl chain length of the surfactant. The
sametrend has been reported for C12 (polysorbate 20) toC18 (polysorbate 80) in nonionic surfactant
wherethe solubilizate is located in the hydrophobic corerather than the oxyethylene region [108].
Attemptshave been made to compare the solubilizingpower of ionic and nonionic surfactants
forsolubilizates which are located in the micellarinterior [109]. In general the solubilizing capacity
forsurfactants with same hydrocarbon chain lengthranked in order of nonionic > cationic >
ionic[105,110]. It is worth to mention that the knowledge ofthe factors that govern the distribution of
nonpolarand amphiphilic solutes between the micelles andthe surrounding aqueous solution is
offundamental importance for the understanding ofthe phenomenon of solubilization [111]. Abu-
Hamdiayyah and Rehman [112] have investigatedthe distribution coefficients of several
amphiphilicadditives as a function of surfactant chain lengthin sodium alkylsulphate. It was found that
thestanders free energy of solubilization for a givenamphiphlie additives decreases with
increasingsurfactant chain length. In a recent study [113]they revealed that distribution coefficient
inpresence of nonpolar additives increases withincreasing surfactant chain length, whichinconsistent to
that found for amphilphilicadditives. This difference in solubilizationtendencies between amphiphilic
and nonpolaradditives was explained as a function of surfactantchain length in terms of the magnitudes
of thevarious contributing terms to the standard freeenergy of solubilization.Moreover, addition of
electrolytes to ionicsurfactants usually causes an increase in micellesize and a decrease in the CMC and
hence anincrease in the solubilizing capacity.Nonelectrolytes which are capable of beingincorporated in
micelle, e.g. alcohol, lead to anincrease in micelle size and hence lead to anincrease in solubilization
[114]. McDonald and Richardson have investigatedthe effect of various concentrations of inorganicsalts
(sodium chloride, magnesium sulphate andmagnesium nitrate) on solubilization of methyland propyl-p-
hydroxybenzoate (methyl andpropylparaben) by a nonionic surfactant(Cetemacrogol) [115]. They found
that in thepresence of the surfactant the total solubilities ofthe esters in the presence of all
concentrations ofinorganic salts were greater than those systemswithout surfactant. However, in all
systems thetotal solubilities in the presence of added salts and

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Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol. 12, No.
4509surfactant are less than the solubilities of theesters in the presence of surfactant alone.
Theyrationalized their findings on the ground thatmicelle size increase in the presence of saltadditives,
then it might be expected that theamount of solutes dissolved would be increasedbecause of larger
volume/surfactant ratios ofmicelles. Additionally, the amount of solubilizationincreases with increasing
temperature [114]. Thisis usually due to increase in solubilizat andincrease of micellar size (particularly
withnonionic ethoxylated surfactants). Goto et al haveexamined the effect of temperature on
thesolubilization of ethylparaben in hexaoxyethylenelauryl ether micelles by gel filtration method.Goto
noted that both enthalpy and entropy effectscontrol the micellar solubilization of
ethylparaben[116].Many techniques have been reported in theliterature for determining partitioning
ofsolubilizates in surfactant solutions. The recenttechniques include vapour pressure
measurements[117-120], voltametric study [121,122],spectroscopic studies (IR, ESR, Raman) [123-128],
neutron scattering [129-134], light scatteringand viscosity [135-138]. Recently the effect of micellar
systems onsolubilization have been useful in wide variety oftechniques, such as separation of
biologicalmicromolecules [139], triplet state photophysic[140,141], drug adsorption [142], and
reactionkinetics [143,144]. They have been also employedas micellar mobile phases to
performchromatographic separations [145-150].REFERENCES[1] K. Shinoda, T. Nakagawa, B.I.
Tamamushiand T. Isemura, Colloidal Surfactants, SomePhysicochemical Properties, AcademicPress, New
York, (1963). [2] M.M. Sckick, Non-ionic Surfactants,Physical Chemistry, Marcel Dekker, NewYork,
(1970).[3] E. Jungermann, Cationic Surfactants,Marcel Dekker, New York, (1970).[4] K.L. Mittal, Solution
Chemistry ofSurfactants, Plenum, New York, (1.2),(1979).[5] J.I. DiStasio, Surfactants, Detergents
andSequestrates, Noyes Data Corp., ParkRidge, N. J., (1981). [6] K.L. Mittal and E.J. Fendler,
SolutionBehaviour Of Surfactants, Plenum, NewYork, (1.2), (1982).[7] T.F. Tadros, Surfactants, Academic
Press,London, (1984).[8] K.L. Mittal and B. Lindman, Surfactants inSolution, Plenum, New York, (1.3),
(1984).[9] M.J. Rosen, Structural PerformanceRelationships in Surfactants, AmericanChemical Society,
Whashington, (1984).[10] R. Zana, Surfactants Solutions, MarcelDekker, New York, (1986).[11] K.L. Mittal
and P. Bothorel, Surfactants inSolution, Plenum, New York, (4.6), (1987).[12] M.J. Rosen, Surfactants in
EmergingTechnologies, Marcel Dekker, New York,(1987).[13] D.T. Wasan and D.O. Shah, Surfactants
inChemical Process Engineering, MarcelDekker, New York, (1988).[14] D. Myers, Surfactant Science
andTechnology, VCH, New York, (1988). [15] M.J. Rosen, Surfactants and InterfacialPhenomena, John
Wiley & sons, New York,2nd ed., (1989).[16] M.R. Porter, Handbook of Surfactants,Blakie, Glasgow,
(1991).[17] S.E. Friberg and B. Lindman, OrganisedSolutions, Surfactants in Science andTechnology,
Marcel Dekker, New York,(1992).[18] R. Sharma, Surfactant Adsorption andSurface Solubilization,
American ChemicalSociety, Whashington, (1995).[19] K.R. Lange, Surfactants ApracticalHandbook,
Hanser, Ohio, (1999).[20] D.O. Hummel, Handbook of SurfactantAnalysis: Chemical, Physicochemical
andPhysical Methods, John Wiley & sons,England, (2000).[21] D.R. Karsa, Surface Active Behavior
ofPerformanceSurfactants,SheffieldAcademic Press, UK, 3, (2000).[22] M.J. Rosen and M. Dahanayake,
IndustrialUtilization of Surfactants: Principles andPractice, AOCS Press, (2000).

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Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 4510[23] V.B. Fainerman,
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