You are on page 1of 22

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


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:;;; ]
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,


‫تﺎﺌ‬.‫تﺎﺒﮐﺮﳌا ﱪﺘﻌًﺗﺎﻴﺤﻄﺳ ﺔﻄﺸﻨﻟاةدﺪﻌﺘﳌا تﺎﻣاﺪﺨﺘﺳﻻا تﺎذ ﺔﻴﺋﺎﻴﻤﻴﮑﻟا تﺎﺒﮐﺮﳌا ﻦﻣ‬i ‫ﺰﺟ ﺪﻌت ﻲﻬﻓ"أﺔﻴﻠﻴﻔﻴﻔﻣ"ﺚﻴﺣءﺎﻤﻠﻟ ﺐﳏ ﺳأر ﻦﻣ‬
‫نﻮﮑﺘت"ﻲﻠﻴﻓورﺪﻴﻫ"ءﺎﻤﻠﻟ ﻫﺮﺎﮐ ﻞ‬i ‫"ًﺎﻴﺤﻄﺳ ﺔﻄﺸﻨﻟا تﺎﺒﮐﺮﻤﻠﻟ ﺔﺟودﺰﳌا ﺔﻌﻴﺒﻄﻟا هﺬًﻫﻻﺎﺼتا ﺎﻬﺘﺒﺴﮐًأﺎ‬.‫ذو"ﰊﻮﻓورﺪﻴﻫ‬i ‫ﻮﻗﳌا ﻞﺜﻣ‬
‫ﺔﺟﺰﺘﻤﳌا ﲑﻏ ﻞﺋاﻮﺴﻟا ﲔﺑﺖ‬i ‫ﺔﻴﺤﻄﺴﻟا تﺎﺮتﻮﺘﻟا ﻦﻣ ﻞﻴﻠﻘﺘﻟا ﻰﻠﻋ ةرﺪﻘﻟا تﺎﺒﮐﺮﳌا هﺬﳍوﺔﺟﺰﺘﻤﳌا ﲑﻏ ﻞﺋاﻮﺴﻟا ﲔﺑ ﻞﺻﺎﻔﻟا‬.‫ﺰﻟاو ءﺎ‬
‫ﺟﺎﺰﺘﻣﻻا ﻰﻠﻋ ﺎ ﺪﻋﺎﺴﻣوﺑ ﻰﻤﺴ‬، ‫ﺢﻄﺴﻟا ﻰﻠﻋ ﺎﻬﻌﻤﺠﺘﺑ ﻚﻟذو ﺔ ﻴﻨﻴﺒﻟاوﻊﻤﺠﺘﻟا ﻊﻴﻄﺘﺴت ﺎ أ ﺎﻤﮐ‬i ‫ﺎﻣ ﻦ‬i ‫ﺔﮐﺮﳊا ﺔﻴﻠﺑﺎﻗ‬، ‫ﻮﮑﻟﳊا ﺮﻓﻮﺘﻟا‬
‫ﺔﻴﻧﺎﺑوﺬﻟا ﻦﻣ ﺪ‬،i ‫ﺰ‬i ‫ﻫﺮوﺪﺑ اﺬﻫو ﺰﻠﺴ‬i ‫ﺎﳌًﺎﺎﻘﺣﻻو يﻮﻴتﺎﺒﮐﺮﻤﻠﻟ يﻮﻴﳊا ﻚﮑﻔﺘﻟاﺔﺒﺋاﺬﻟا ﲑﻏ وأ ﺔﻫرﺎﮑﻟا ﺔ‬i ‫ًﺎﻴﺤﻄﺳ ﺔﻄﺸﻨﻟا‬.‫ﻮﻀﻌﻟا‬
‫تﺎﺒﮐﺮﳌا ﻦﻋ ﺔﻤ ﻴﻗ تﺎﻣﻮﻠﻌﻣ مﺪﻘ‬i ‫ﺔ‬-‫ﺔﻴﻌﺟﺮﳌا ﺔﻻﻘﳌا هﺬﻫ ﻦﻣ ﻟﻮﻷا ءﺰﳉاﻦﻣﻪﺿاﺮﻌﺘﺳا لﻼﺧ‬i ‫و ﺔﻌﻴﺒﻄﻟا ﰲ تﺎﺒﮐﺮﳌا هﺬﻫ‬-‫اﺪﺒﻟا ﰲ‬
‫ﺪﺟاﻮﺘﻻﻔﻴﻨﺼترﻮﻄﺘﻟا ﻰﻠﻋ ءﻮﻀﻟا ﻲﻘﻠ‬i ‫ًاﲑﺧًأاﺮﺧآ ﺲﻴﻟوﰲ تﺎﺒﮐﺮﳌا هﺬﳍ‬.‫ﰒ ﻦﻣو ﺔﻣﺎﻌﻟا ﺎﻲﺋﺎﻴﻤﻴﮑﻟاﺐﺣﺎﺻ يﺬﻟارﻮﻄتتﺎﺒﮐﺮﳌا هﺬﻫ‬
‫ﺔﻴﺋﺎ‬i ‫ﺰﻴﻔﻟا تﺎﻔﺼﻟا ﻢﻫأ ﻞﻴﺼﻔﺘﻻﺑو ءﺰﳉا اﺬﻫ ﺶﻗﺎﻨ‬i ‫ﻣاﻮﻌﻟا ﻢﻫأ ﻰﻠﻋ ﺪﻴﮐأﺘﻟا لﻼﺧ ﻦﻣ ﺔﻴﺋﺎﻨﺜﺘﺳﻻا ﲑ‬i ‫ﺎﻌﳌا هﺬﻫ ﺎﻬﺘﺒﺴﮐأ ﱵﻟاو‬
‫ﻞﻴﻻﶈاتﺎﻔﺼﻟا 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

Page 2

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].


Page 3

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.


Page 4
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).


Page 5

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-
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


Page 6

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.


Page 7

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.


Page 8

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


Page 9

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


Page 10
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


Page 11

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,
(CH2)11N(CH3)2O0.087CH3(CH2)11(OCH2CH2)6OHTable 6: The effect of the
number of ionic groups on the CMC.103 CMC
H(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]. 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].


Page 12

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. 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].
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) CMC,(M)
Cetylpyridinium chloride[NaCl],(M)0.01750.05840.4380.730103 CMC,


Page 13

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 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].


Page 14

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


Page 15

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


Page 16

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.


Page 17
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.


Page 18

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


Page 19

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.


Page 20

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


Page 21

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).


Page 22

Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No.
4510[23] V.B. Fainerman, D. Möbius and R.
Miller,Surfactants:Chemistry,Interfacialproperties and Applications,
Elsevier,Amsterdam, (2001).[24] A.E. Hargreaves, Chemical Formulation:An
Overview of Surfactants-BasePreparations Used in Everyday Life, Theroyal society of
Chemistry, UK, (2003); D.R. Karsa, Surfactants in Polymers, Coating,Inks and
Adhesives, Blackwell, Oxford,(2003).[25] J. Goodwin, Colloids and Interfaces
withSurfactants and Polymers: An Introduction,John Wiley & sons, England, (2004).
[26] M. Ash and I. Ash, Handbook of IndustrialSurfactants, 4th Ed., Synapse
InformationResources, New York, (2005).[27] S.A. Ostroumov, Biological Effects
ofSurfactants, Taylor& Fancis, New York,(2006).[28] R.J. Farn, Chemistry and
Technology ofSurfactants, Blackwell, Oxford, (2006).[29] M. Drew, Surfactant
Science andTechnology, 3ed. Ed., John Wiley & sons,New Jersey, (2006).[30]
Surfactant Science Series, Marcel Dekker,New York, vol. 1-133, (1966-2007).[31] G.
Biresaw and K.L. Mittal, Surfactants inTribology, Taylor & Francis, New York,(2008).
[32] M.J. Rosen, CHEMTECH, 292, (1985).[33] Y. Chevalier, Curr. Opin. Colloid
InterfaceSci., 7, 3 (2002).[34] B.R. Pradip, Colloids Surf. A, 205, 139(2002).[35] S.
Bhattacharya and J. Haldar, ColloidsSurf. A, 205, 119 (2002).[36] G. Kume, M.
Gallotti and G. Nunes, J.Surfactants Deterg., 11(1), 1 (2008).[37] T.F. Tadros,
Applied Surfactants Principlesand Applications,Wiley-VCH, London,(2005).[38] C. E.
Stevens, in Kirk-Othmer Encyclopediaof Chemical Technology, Wiley, New York,NY,
2nd ad., 19, 507 (1969).[39] I. Shah and L.G. Henscheid, J. Chem.Educ.,60, 865
(1983).[40] D. Stigter, J. Phys. Chem., 29, 1008 (1975)[41] C.A. Bunton and L.S.
Romsted, MicellarEffects Upon Decylation, in The Chemistryof Acid Derivatives, ed.
S. Patai, JohnWiley and sons, New York, 945 (1984). [42] L.L. Schramm, E.N. Stasiuk
and D.G.Marangoni, Annu. Rep. Prog. Chem. Sect.C., 99, 3 (2003).[43] J.H. Clint,
Surfactant Aggregation, Ph.D.,Chapman & Hall, New York (1992).[44] McCutcheon,
Detergents and Emulsifiers,Allied Publishing Co., New Jersey,published annually.
[45] N.M. Os van, J.R. Haak and L.A.M. Rupert,Physich-chemical Properties of
SelectedAnionic, Cationic and Nonionic Surfactants,Elsevier, Amsterdam, (1993).
[46] R.M. Hill, Silicon Surfactants, SurfactantScience Series, Marcel Dekker, New
York,86, (1999).[47] E. Kissa, Fluorinated Surfactants andRepellents, 2ndEd.,
Surfactant ScienceSeries, Marcel Dekker, New York, 97,(2001). [48] A. Singh, J.D.V.
Hamme and O.P. Ward,Microbiol. Mol. Bio. Rev., 69, 99 (2006).[49] H.C. Evans, J.
Chem Sic, 579 (1956).[50] A.J. Stirton J.K. Weil and R.G. Bistline Jr.,J. Am. Oil Chem.
Soc., 31, 13 (1953).[51] J.K. Weil and A.J. Stirton, J. Am. Oil Chem.Soc., 34, 899
(1956).[52] B. Gabard, E. Chatelain, E. Bieli and S.Haas, Skin Res. Technol., 7, 49
(2001).[53] L. Mu and S.S. Feng, J. Controlled Release,80, 129, (2002).[54] R.C.
Bazito and O.A. El Seoud, Langmuir,18, 4362 (2002).[55] K. Esumi and M. Ueno,
Structure-Performance Relationships in Surfactants,Dekker, New York, (1997).[56]
F.M. Menger and C.A. Littau, J. Am. Chem.Soc., 113, 1451 (1991).[57] F. M. Menger
and C. A. Littau, J. Am.Chem. Soc., 115, 10083 (1991).[58] M.J. Rosen and D.J. Tracy,
J. SurfactantsDeterg., 1, 547 (1998).[59] F.M. Menger and J.S. Keiper, Angew.Chem.
Int. Ed., 39, 1906 (2000).[60] R. Zans, J. Colloid Interface Sci., 248, 203(2002).[61]
R. Zana and J. Xia,Gemini Surfactants:Synthesis, Interfacial and Solution-
Phasebehavior, and Applications, Surfactant


Page 23

Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol.
12, No. 4511Science Series, Marcel Dekker, New York,117, (2004).[62] A.M.
Goncalves, A.P. Serro, M.R. Aires-Barros, J. M. S. Cabral, Prot. Struc. Molec.Enzym.,
1480(1), 91 (2000).[63] P.H.H. Hermkens, H.C.J. Ottenjheijm andD. Rees,
Tetrahedron, 52, 4527 (1996).[64] M.A. Desando and L.W. Reeves, Can. J.Chem., 64,
1817 (1986).[65] J.H. Fendler and E.J. Fendler, Catalysis inMicellar and
Macromolecular Systems,Academic Press, New York, (1975). [66] P. Mukerjee and
K.J. Mysels, CriticalMicelle Concentration of Aqueoussurfactant Systems, Data Sevr.
Natl. Bur.Stand. U. S. 36, US Government PrintingOffice, Washington D.C, (1971).
[67] C.E. Lin, J. Chromatogr. A, 1037, 467(2004).[68] L. Yu, M. Tan, B. Ho, J.L. Ding
and T.Wohland, Anal. Chim. Acta, 556, 216(2006).[69] D.F. Evans and P.J.
Wightman, J. ColloidInterface Sci, 86, 515 (1982).[70] K. Shinoda, M. Kobayashi and
N.Yamaguchi, J. Phys. Chem., 91, 5292(1987)[71] D.G. Atcher, H.J. Albert, D.E. White
andR.H. Wood, J. Colloid Interface Sci, 100, 68(1984). [72] C. La. Mesa, B. Sesta,
M.G. Bonicelli andG.F. Ceccaroni, Langmuir, 6, 728 (1990).[73] G. Sugihara and P.
Mukerjee, J. Phys.Chem., 85, 1612 (1981).[74] T.S. Brun, H. Hoiland and E.
Vikingstad, J.Colloid Interface Sci, 63, 89 (1978).[75] S. Kaneshina, M. Tanaka, T.
Tomida and R.Matuura, J. Colloid Interface Sci, 48, 450(1974).[76] L.L. Schramm,
D.B. Fisher, S. Schurch andA. Cameron, Colloids Surf., 94, 154 (1995).[77] E.N.
Stasuik and L.L. Schramm, J. ColloidInterface Sci, 178, 324 (1996).[78] C. Morrison,
L.L. Schramm and E.N.Stasuik, J. Petrol. Sci. Eng., 15, 91 (1996). [79] L.L. Schramm,
Surfactants, Fundamentaland applications in Petroleum IndustryCambridge
University Press, Cambridge,UK, (2000). [80] P.H. Elworthy, A.T. Florence and
C.B.Macfarlane, Solubilization by SurfaceActive Agents and Its Applications
inChemistry and The Biological Scince, Chapman & Hall, London (1968).[81] K.
Holmberg, B.J. Onsson, B. Kronberg andB. Lindman, Surfactants and Polymers
inAqueous Solutions, 2nd ed., John Wiley &Sons, Chichester, (2004).[82] P.
Mukerjee, Adv. Colloid. Interface Sci., 1,241 (1967).[83] D.A. Doughty, J. Phys.
Chem., 87, 5286(1983) [84] P. Mukerjee, K.J. Mysels and P.J. Kapauan,J. Phys.
Chem., 71, 4166 (1975)[85] D. Stigter, J. Phys. Chem., 68, 3603 (1964)[86] J.E.
Brady, D.F. Evans, G.G. Warr, F.Grieser and B.W. Ninham, J. Phys. Chem.,90, 4166
(1986).[87] J. Gettins, R. Greenwood, J.E. Rassing andE.J. Nyn. Jones, Chem. Soc.
Chem. Comm.,24, 1030 (1976). [88] M.J. Schick, J. Colloid Sci., 17, 801 (1962);J.
Phys. Chem., 68, 3585 (1964).[89] M.J. Schick and A.H. Gilbert, J. ColloidSci., 20, 464
(1965).[90] S. Parades, M. Tribout, J. Ferreira and J.Leonis, J. Colloid and Polymer
Sci., 254,637 (1976).[91] M.J. Schick, J. Phys. Chem., 68, 3585(1964).[92] E.J.R.
Sudhoelter andJ. B.F.N. Engbert, J.Phys. Chem., 83, 1854 (1979). [93] B. Lindman,
Surfactants, (T, F. Tadros, ed.),Academic Press, London, Chap. 4 (1984). [94] N.
Nishido, Y. Moroi and R. Matura, Bull.Chem. Soc. Jpn.,47, 2634 (1974). [95] M.
Kodama, R. Boku, T. Ishida and M.Miura, Bull. Chem. Soc. Jpn., 50, 751(1979).[96] S.
Hartland, Surface and InterfacialTension: measurement, Theory andApplications,
Surfactant Science Series,Marcel Dekker, New York, 119, (2004).[97] J.S. Clunie, J.F.
Goodman and B.T. Ingram,in Surface and Colloid Science, ed, E.Matijevic, Wiley,
New York, 3, 167(1971).[98] K. Shinoda, T. Nakagawa, B.I. Tamamushiand T.
Isemura, Colloidal Surfactants, Some


Page 24

Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No.
4512Physicochemical Properties, academicPress, New YorK, (1963).[99] S. Kumar,
D. Sharma, Z.A. Khan andKabir-ud-Din, Langmuir, 18, 4205 (2002).[100] P.M.
Kruglyakov, Hudrophile-LipophileBalance of Surfactants and Soild Particles,Elsevier,
Amsterdam, (2000).[101] A. Wadlle, H. Tesmann, M Leonard and T.Förster, in
Surfactants in Cometics, ed. M.M. Rieger and L.D. Hhein, Dekker, NewYork, 2nd ed.,
207 (1997). [102] K. Esumi and M. Ueno, Structure-Performance Relationships in
Surfactants,2nd Ed., Surfactant Science Series, MarcelDekker, New York, 112,
(2003).[103] J.N. Israelachivil, International and SurfaceForces, with Applications to
Colloidal andBiological Systems, Academic Press, 247(1985).[104] C. Tandford, The
hydrophobic effect, 2ndad., John Wiley & sons, New York, (1980).[105] D. Attwood,
and A.T. Florence, SurfactantSystem. Their Chemistry, Pharmacy andBiology,
Chapman & Hall, London (1983). [106] F.M. Menger, Acc. Chem. Res., 12,
111(1979).[107] R. Nagarajan and E. Ruckenstein, SurfactantSolution, ed. K.L. Mittal
Lindman, 423(1984).[108] A.A. Ismail, M.W. Gouda and M.M.Motanic, J. Pharm. Sci.,
59, 220 (1970).[109] H. Schott J. Pharm. Sci., 71, 3611 (1967). [110] P.A. Bhat, A.A.
Dar and G.M. Rather,Chem, Eng., Data, 53(6), 1271 (2008).[111] R. Nagarajan, M.
Chaiko and E.Ruckenstein, J. Phys. Chem., 88, 2916(1984).[112] M. Abu-Hamidiyyah
and I.A. Rahman, J.Phys. Chem., 89, 2377 (1985).[113] M. Abu-Hamidiyyah, and I.A.
Rahman, J.Phys. Chem., 91, 2377 (1987)[114] T.F. Tadros, The Surfactants, (T.F.
Tadrosed.), Academic Press, London, (1984). [115] C. McDonald and C. Richardson,
J. Pharm.Pharmacol., 33, 38 (1981).[116] A. Goto, F. Endo and T. Higashino,
Chem.Pharm. Bull. Japn., 32, 2905 (1984).[117] J. Bosch, F. Strozzi, T.J. Snee, J. A.
Hareand J.M. Zaldivar, J. Loss Prev. Proce.Indust., 17(6), 389 (2004). [118] M.
Nedyalkov, L. Alexandrove, D.Platikunov, B. Levecke and T.F. Tadros,Colloid &
Polymer Sci., 286, 713 (2008).[119] R. Sadeghi and B. Goodarzi, Biophys.Chem.,
135, 116 (2008).[120] W.S. Drisdell, C.D. Cappa, J.D. Smith, R.J.Saykally and R.C.
Cohen, Atoms. Chem.Phys. Disscuss., 8, 8565 (2008).[121] Z. Wei and P.
Somasundaran, J. Appl.Elect., 34(2), 241 (2004).[122] L. Ming, X. Xi, T. Chen and J.
Liu, Sensors,8, 1890 (2008).[123] S. Isskike and Y. Yza, Bull. Chem. Soc.Jpn., 54,
3205 (1981). [124] J. Oakes, P. Gratton and T. Gardon-Smith,Dyes and Pigments,
46(3), 169 (2000).[125] C.M. Fetzer and R.T. Lee, D.C. Chapmanand G.B. String
Fellow, J. Appl. Phys.,90(2), 1040 (2001)[126] J. Oakes, P. Gratton and S. Dixon,
ColorTechnology, 119(5), 301 (2003).[127] H.P. He, Q. Zhan, R.L. Frast, B.J.
Wood,L.V. Dung and J.T. Kloprogge, Spectro.Acta A, 66, 1180 (2007).[128] A.
Chakrabory and S. Basak, Colloids Surf.B Biointerfaces, 63(1), 83 (2008).[129] M.
Bergström, J. Phys. Chem. B., 104(17),4155 (2000).[130] K.S. Sharma, J.V. Joshi, V.K.
Aswal. P.S.Goyal and A.K. Rakshit, Pramana, 63(2),297 (2004).[131] A. Paul. P.C.
Griffiths, E. Pettrtsson, P.Stilbs, L.B. Barney and R. Zana, J. Phys.Chem. B, 109(33),
15775 (2005). [132] S. Chdankar, V.K. Aswal, J. Kahlbrecher,R. Vavrin and A.G.
Wagh, J. Phys.:Condens. Matter, 19, 12 (2007). [133] R. Mukhopdhyay and S.L.
Chaplot, Curr.Sci., 94(11), 358 (2008).[134] D.M. Kuntz and L.M. Walker, Soft
Matter,4, 286 (2008).[135] S. Marchetti and G. Onori, J. Phys. Chem.B, 109(8), 3676
(2005)[136] Y.F.O. Yang, Y.S. Wang, X.W. Mi, J.H.Xue and X. Wang, Anal. Sci., 23(5),
533(2007),[137] A. Zaccone, H. Wu, M. Lattuada and M.Morbidelli, J. Phys. Chem. B,
112(7), 1976(2008).


Page 25

Surfactants: Part 1: Overview On Their Physical PropertiesJ. Saudi Chem. Soc., Vol.
12, No. 4513[138] X. Guo, H. Li, F. Zhang, S. Zheng and R.Guo, J. Colloid Interface
Sci., 324, 185(2008).[139] P.A. Albertson, J. Chromatogr., 159, 111(1978).[140] R.A.
Femia and L.J. Clinelone, Anal.Chem., 56, 327 (1984). [141] T. Piok, C. Grademaier,
F.P. Wenz, S. Patil,R. Montenegro, K. Landfester, G. Lanzani,G. Cerullo, U. Scherf and
E.J.E. List, Chem.Phys. Lett., 389, 7 (2004).[142] M. Wang, J.W. Yan, Y.F. Lin, J.D. Lu
andX.Y. Fu, Chin. Chem. Lett., 13(12), 1203(2002).[143] E. Pelizzetti and E.
Pramauro, J. Phys.Chem., 88, 990 (1984).[144] M.N. Khan, Micellar Catalysis,
SurfactantScience Series, Taylor & Francis, NewYork, 133, (2007).[145] A. Berthod
and C. Garcia-Alvarez-Coque,Micellar Liquid Chromatography, MarcelDekker, New
York, (2000).[146] Z. Chen, K. Yamada, M. Niitsuma, K.Uchiyama and T. Hobo,
Chromatographia,54, 629 (2001)[147] J. Zhu, J. Surf. & Detergents, 7(4), 421(2004).
[148] S.X. Gong, T. Bo, L. Huang, K.A. Li andH.W. Liu, Chin. Chem. Lett., 15(9),
1063(2004).[149] K. Kim and D. Kim, J. App. Poly. Sci.,96(1), 200 (2005).[150] V.P.
Schnee and C.P. Palmer,Electrophoresis, 29(4), 777 (2008).


Page 26

Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 4514