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 Eects 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,
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. Abstract: Surfactants are among the most versale chemical compounds. They are amphiphilic molecules composed of a hydrophilic head and a hydrophobic tail. This dual nature of the surfactants produces a strong anity for interfaces between immiscible uids such as oil and water. Surfactants can reduce surface and interfacial tensions by accumulang at the interface of immiscible uids to form micelles and increase the solubility, mobility, bioavailability and subsequent biodegradaon of hydrophobic or insoluble organic compounds. Part 1 of this review aords valuable informaon about the surfactants starng with their natural occurrence and general classicaon. Then it adds addional light on the chemistry development of these compounds. Last but not least it discusses in detail the most important physical properes of these compounds in the soluons, which gave them their extraordinary criteria, by emphasizing on the factors that aect on these properes. Keywords: Surfactants; Micelles; Crical micelle concentraon CMC; Micellar shape; Solubilizaon, Reversed micelles, Aggregaon number, Kra point, HLB.Contents page 1 Introducon490 2Surfactants490 3Natural surfactants 4914General classicaons of surfactants4925The development of surfactant chemistry4926Physical properes of surfactants4946.1Micellar formaon4946.1.1Normal micellar formaon4946.1.2Reversed micellar formaon495* To whom all correspondence should be addressed --------------------------------------------------------------------------------Page 2
Hamad A. Al-Lohedan and Fawzia F. Al-BlewiJ. Saudi Chem. Soc., Vol. 12, No. 44906.2Crical micelle concentraon CMC4956.2.1Factors aecng crical micelle concentraon CMC4976.2.1.1Hydrocarbon chain length and structure4976.2.1.2Nature of the polar head group4986.2.1.3The eect of counterion4996.2.1.4The eect of addives5006.2.1.5The eect of the temperature5006.2.1.6The eect of pressure5016.3Surfactant and interfacial tension5016.4The Kra and cloud point5026.5The HLB concept5026.6Micellar structure and shape5046.7Aggregaon number5066.8Solubilizaon in aqueous micellar soluon508References5091. INTRODUCTIONThe widespread importance of surfaceacve agents (usually referred to as surfactants)in praccal applicaons, and scienc interest intheir nature and properes, have precipitated awealth of published literature on the subject [1-31]. Over the past ten years, new surfactantsmolecules have been appearing at a relavelyrapid pace. This growth in surfactant synthesis hasparalleled the emphasis on increasing the basicperformance of surfactant formulaons and theprovision of new surfactant technology to adiverse range of disciplines. Although surfactantscience is now a reasonably mature discipline,there is a sll room for new moleculesdesignedfor specic purposes and new applicaons (suchas nanoparcle synthesis and more diverse andenvironmentally friendly consumer products).These new materials have spurred on the quest forimprovedmolecularmodels,computersimulaons and improved structure-acvityrelaonships. New funconalized surfactantsdepend crically on the nature and placement ofaddional groups. Slight modicaons of themolecular structure with respect to convenonalsurfactants lead to a rich morphology of structuresthat are being explored by increasingly moresophiscated techniques and , in turn, enhancingour understanding of their properes 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 properes in thesoluons and at interfaces. 2 SurfactantsSurfactants are amphipathic molecules thatconsist of a nonpolar hydrophobic poron, usuallya straight or branched hydrocarbon oruorocarbon chain containing 8-18 carbon atoms,which is aached to a polar or ionic poron(hydrophilic). The hydrophilic poron can,therefore be nonionic, ionicor zwierionic, andaccompanied by counter ions in the last two cases[37]. These compounds are termedsurfactants,amphiphiles, surface-acve agents, tensides, or, inthe very old literature, paran-chain salts. Themost commonly used term, surfactant, wasoriginally registered as a trademark for selectedsurface-acve products and later released to thepublic domain [38]. The adsorpon of thesesurfactants at gas/liquid and liquid/liquid interfacehas long been recognized as key factor in widevariety of praccal applicaons areas which areillustrated in terms of mineral and petroleumprocessing, biological systems, pharmaceucals,health, personal care products, foods and cropsproducon. Owing To their tendency to beadsorbed at interface, they are oen called assurface acve agents or colloidal surfactants. Theyundergo self-associaon resulng 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 ProperesJ. Saudi Chem. Soc., Vol. 12, No. 4491The unusual properes of aqueous surfactantsoluons 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 interacons [42].3 Natural SurfactantsIt is not exaggeraon 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 arederivaves of glycerol esters with long-chain fayacids, Table 1 [43]. In milk, the fat is mainly in the form origlycerides but a small amount is present asphospholipids and diglycerides, which aresurfactants that help to stabilize the emulsion inwater. During digeson fats are converted intomore soluble species, which can be transportedaround the body more readily. A variety ofsurfactants are involved at dierent stages duringthis digesve 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 fayacids leave these surfactant complexes to combinewith proteins such as serum albumin to formlipoproteins, which self-organize into speciessuitable for transport to various desnaonsaround 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 membraneFay acidsR–CO–OHSebum IntesnesBile saltsNHCH2COO-Na+OHHOOHOSodium glycocholateGall-bladderIntesnes*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 Classicaons of SurfactantsA simple classicaon of surfactants basedon the nature of the hydrophilic group iscommonly used. The main classes may be disn-guished, namely anionic, caonic, 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 properes ofselected anionic, caonic and nonionic surfactants[45]. In addion, another class of surfactants,usually referred to as polymeric surfactants, haslong been used for the preparaon of emulsionsand suspensions and their stabilizaon [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 somemes referred to as superweers as theycause enhanced weng and spreading of theiraqueous soluon. However, they much moreexpensive than convenonal surfactants and areonly applied for specic applicaons whereby thelow surface tension is a desirable property [37].Biosurfactants are surface acve compoundsproduced by microorganisms. Most microbialsurfactants are complex molecules,
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