Surfactant

Surfactants are compounds that lower the surface tension (or interfacial tension) between two liquids or between a liquid and a solid. Surfactants may act as detergents, wetting agents, emulsifiers, foaming agents, and dispersants.

Etymology and definition

The term surfactant/surfactants is a blend of surface active agents.[1] n nde! "edicus and the #nited States $ational %ibrary of

"edicine, surfactant/surfactants is reser&ed for the meaning pulmonary surfactant. 'or the more general meaning,surface active agent/s is the heading.

( micelle ) the lipophilic tails of the surfactant ions remain on the inside of the micelle due to unfa&ourable interactions. The polar *heads* of the micelle, due to fa&ourable interactions with water, form ahydrophilic outer layer that in effect protects the hydrophobic core of the micelle. The compounds that ma+e up a micelle are typically amphiphilic in nature, meaning that micelles are soluble not only in protic sol&ents such as water but also in aprotic sol&ents as a re&erse micelle.

Composition and structure

Surfactants are usually organic compounds that are amphiphilic, meaning they contain both hydrophobic groups (their tails) andhydrophilic groups (their heads).[,] Therefore, a surfactant contains both a water insoluble (or oil soluble) component and a water soluble component. Surfactants will diffuse in water and adsorb at interfaces between air and water or at the interface between oil and water, in the case where water is mi!ed with oil. The insoluble hydrophobic group may e!tend out of the bul+ water phase, into the air or into the oil phase, while the water soluble head group remains in the water phase. This alignment of surfactants at the surface modifies the surface properties of water at the water-air or water-oil interface. .orld production of surfactants is estimated at 1/ "ton-y, of which about half are soaps. 0ther surfactants produced on a particularly large scale
[5]

are linear +ton-y), fatty

al+ylben1enesulfonates (1233

+ton-y), lignin

sulfonates (433

alcohol etho!ylates (233 +tons-y), andal+ylphenol etho!ylates (/33 +ton-y).

Sodium stearate, the most common component of most soap, which comprise about /36 of commercial surfactants.

78(/89odecyl) ben1enesulfonate, a linear dodecylben1enesulfonate, one of the most common surfactants.

Structure of surfactant phases in water

n the bul+ aqueous phase, surfactants form aggregates, such as micelles, where the hydrophobic tails form the core of the aggregate and the hydrophilic heads are in contact with the surrounding liquid. 0ther types of aggregates such as spherical or cylindrical micelles or bilayers can be formed. The shape of the aggregates depends on the chemical structure of the surfactants, depending on the balance of the si1es of the hydrophobic tail and hydrophilic head. This is +nown as the :%;, :ydrophilic8lipophilic balance. Surfactants reduce the surface tension of water by adsorbing at the liquid8gas interface. The relation that lin+s the surface tension and the surface e!cess is +nown as the <ibbs isotherm.

Dynamics of surfactants at interfaces

The dynamics of adsorption of surfactants is of great importance for practical applications such as foaming, emulsifying or coating processes, where bubbles or drops are rapidly generated and need to be stabili1ed. The dynamics of adsorption depends on the diffusion coefficient of the surfactants. ndeed, as the interface is created, the adsorption is limited by the diffusion of the surfactants to the interface. n some cases, there e!ists a barrier of energy for the adsorption or the desorption of the surfactants, then the adsorption dynamics is +nown as =+inetically limited>. Such energy barrier can be due to steric or electrostatic repulsions. The surface rheology of surfactant layers, including the elasticity and &iscosity of the surfactant layers plays a &ery important role in foam or emulsion stability.

Characterization of interfaces and surfactant layers

nterfacial and surface tension can be characteri1ed by classical methods such as the 8pendant or spinning drop method. 9ynamic surface tensions, i.e. surface tension as a function of time, can be obtained by the "a!imum ;ubble ?ressure apparatus The structure of surfactant layers can be studied by ellipsometry or @8Aay reflecti&ity. Surface rheology can be characteri1ed by the oscillating drop method or shear surface rheometers such as double8cone, double8ring or magnetic rod shear surface rheometer.

Detergents in biochemistry and biotechnology

n solution, detergents help solubili1e a &ariety of chemical species by dissociating aggregates and unfolding proteins. ?opular surfactants in the biochemistry laboratory are S9Sand BT(;. 9etergents are +ey reagents to e!tract protein by lysis of the cells and tissuesC They disorgani1e the membrane>s lipidic bilayer (S9S, Triton @8133, @8 117, B:(?S,90B, and $?873), and solubili1e proteins. "ilder detergents such as (0ctylThio<lucosides) are used to solubili1e sensible proteins (en1ymes, receptors). $on8 solubili1ed material is har&ested by centrifugation or other means. 'or electrophoresis, for e!ample, proteins are classically treated with S9S to denature the nati&e tertiary and quaternary structures, allowing the separation of proteins according to their molecular weight. 9etergents ha&e also been used to decellularise organs. This process maintains a matri! of proteins that preser&es the structure of the organ and often the micro&ascular networ+. The process has been successfully used to prepare organs such as the li&er and heart for

transplant in rats.[7] ?ulmonary surfactants are also naturally secreted by type lung al&eoli in mammals.

cells of the

Classification of surfactants
The *tail* of most surfactants are fairly similar, consisting of a hydrocarbon chain, which can be branch, linear, or aromatic. 'luorosurfactants ha&e fluorocarbon chains. Silo!ane surfactants ha&e silo!ane chains. "any important surfactants include a polyether chain terminating in a highly polar anionic group. The polyether groups often comprise etho!ylated (polyethylene o!ide8li+e) sequences inserted to increase the hydrophilic character of a surfactant. ?olypropylene o!ides con&ersely, may be inserted to increase the lipophilic character of a surfactant. Surfactant molecules ha&e either one tail or twoD those with two tails are said to be doublechained.

Surfactant classification according to the composition of their headC nonionic, anionic, cationic, amphoteric. "ost commonly, surfactants are classified according to polar head group. ( non8ionic surfactant has no charge groups in its head. The head of an ionic surfactant carries a net charge. f the charge is negati&e, the surfactant is more specifically called anionicD if the charge is positi&e, it is called cationic. f a surfactant contains a head with two oppositely charged groups, it is termed 1witterionic. Bommonly encountered surfactants of each type includeC

Anionic

Sulfate, sulfonate, and phosphate esters

(nionic surfactants contain anionic functional groups at their head, such sulfates as sulfate, sulfonate, phosphate, and carbo!ylates. ?rominent al+yl

include ammonium lauryl sulfate, sodium lauryl sulfate (S9S, sodium dodecyl sulfate, another name for the compound) and the related al+yl8ether sulfates sodium laureth sulfate, also +nown as sodium lauryl ether sulfate (S%ES), and sodium myreth sulfate. 9ocusatesC dioctyl sulfosuccinate, perfluorooctanesulfonate (?'0S), perfluorobutanesulfonate,linear al+ylben1ene sulfonates (%(;s). These include al+yl8aryl ether phosphates and the al+yl ether phosphate sodium

Carboxylates
These are the most common surfactants and comprise the al+yl carbo!ylates (soaps), such as sodium stearate. "ore speciali1ed species include sodium lauroyl sarcosinate and carbo!ylate8based fluorosurfactants such as perfluorononanoate, perfluorooctanoate (?'0( or ?'0).

Cationic head groups

p:8dependent primary, secondary, or tertiary aminesC ?rimary and secondary amines become positi&ely charged at p: F 13C[/]

0ctenidine dihydrochlorideD ?ermanently charged quaternary ammonium cationC (l+yltrimethylammonium saltsC cetyl trimethylammonium bromide (BT(;) a.+.a. he!adecyl trimethyl ammonium bromide, cetyl trimethylammonium chloride (BT(B)

Betylpyridinium chloride (B?B) ;en1al+onium chloride (;(B) ;en1ethonium chloride (;GT) /8;romo8/8nitro81,58dio!ane 9imethyldioctadecylammonium chloride Betrimonium bromide 9ioctadecyldimethylammonium bromide (909(;)

Zwitterionic surfactants
Gwitterionic (amphoteric) surfactants ha&e both cationic and anionic centers attached to the same molecule. The cationic part is based on primary, secondary, or tertiary amines or quaternary ammonium cations. The anionic part can be more &ariable and include sulfonates, as in B:(?S (58[(58Bholamidopropyl)dimethylammonio]818propanesulfonate). 0ther anionic groups are sultaines illustrated by cocamidopropyl hydro!ysultaine. ;etaines, e.g., cocamidopropyl betaine. ?hosphatesC lecithin

Nonionic surfactant
"any long chain alcohols e!hibit some surfactant properties. ?rominent among these are the fatty alcohols cetyl alcohol, stearyl alcohol, and cetostearyl alcohol (consisting predominantly of cetyl and stearyl alcohols), and oleyl alcohol.

?olyo!yethylene glycol al+yl ethers (;riH)C B:5)(B:,)13)14)(08B,:7)1),/)0:C 0ctaethylene glycol monododecyl ether ?entaethylene glycol monododecyl ether ?olyo!ypropylene glycol al+yl ethersC B:5)(B:,)13)14)(08B5:4)1),/)0 <lucoside al+yl ethersC B:5)(B:,)13)14)(08<lucoside)1)5)0:C 9ecyl glucoside, %auryl glucoside 0ctyl glucoside ?olyo!yethylene glycol octylphenol ethersC BI:12)(B4:7))(08B,:7)1),/)0:C Triton @8133 ?olyo!yethylene glycol al+ylphenol ethersC BJ:1J)(B4:7))(08B,:7)1),/)0:C $ono!ynol8J <lycerol al+yl estersC <lyceryl laurate ?olyo!yethylene glycol sorbitan al+yl estersC ?olysorbate Sorbitan al+yl estersC Spans Bocamide "E(, cocamide 9E( 9odecyldimethylamine o!ide

;loc+ copolymers of polyethylene glycol and polypropylene glycolC ?olo!amers ?olyetho!ylated tallow amine (?0E().

According to the composition of their counter ion

n the case of ionic surfactants, the counter8ion can beC

"onoatomic - norganicC

BationsC metals C al+ali metal, al+aline earth metal, transition metal (nionsC halidesC chloride (BlK), bromide (;rK), iodide ( K) ?olyatomic - 0rganicC BationsC ammonium, pyridinium, triethanolamine (TE() (nionsC tosyls, trifluoromethanesulfonates, methylsulfate

Current mar!et and forecast

The annual global production of surfactants was 15 million metric tons in ,33I, and the annual turno&er reached #SL,7.55 billion in ,33J, nearly ,6 up from the pre&ious year. The mar+et is e!pected to e!perience quite healthy growth by ,.I6 annually to ,31, and by 5./) 76 thereafter.[4][2] Specialists e!pect the global surfactant mar+et to generate re&enues of more than #SL71 billion in ,31I ) translating to an a&erage annual growth of 7./6[I]

"ealth and en#ironmental contro#ersy

Surfactants are routinely deposited in numerous ways on land and into water systems, whether as part of an intended process or as industrial and household waste. Some of them are +nown to be to!ic to animals, ecosystems, and humans, and can increase the diffusion of other en&ironmental contaminants. [J][13][11] (s a result, there are proposed or &oluntary restrictions on the use of some surfactants. 'or e!ample, ?'0S is a persistent organic pollutant as Hudged by the Stoc+holm Bon&ention. (dditionally, ?'0( has been subHect to a &oluntary agreement by the #.S. En&ironmental ?rotection (gency and eight chemical companies to reduce and eliminate emissions of the chemical and its precursors.[1,] The two maHor surfactants used in the year ,333 were linear al+ylben1ene sulfonates (%(S) and the al+yl phenol etho!ylates ((?E). They brea+ down in the aerobic conditions found in sewage treatment plants and in soil.[15] 0rdinary dishwashing detergent, for e!ample, will promote water penetration in soil, but the effect would last only a few days (many standard laundry detergent powders contain le&els of chemicals such as al+ali and chelating agents that can be damaging to plants and should

not be applied to soils). Bommercial soil wetting agents will continue to wor+ for a considerable period, but they will e&entually be degraded by soil micro8organisms. Some can, howe&er, interfere with the life8cycles of some aquatic organisms, so care should be ta+en to pre&ent run8off of these products into streams, and e!cess product should not be washed down.[citation needed] (nionic surfactants can be found in soils as the result of sludge application, wastewater irrigation, and remediation processes. Aelati&ely high concentrations of surfactants together with multimetals can represent an en&ironmental ris+. (t low concentrations, surfactant application is unli+ely to ha&e a significant effect on trace metal mobility. [17][1/]

$iosurfactants
$iosurfactants are surface8acti&e substances synthesised by li&ing cells. nterest in microbial surfactants has been steadily increasing in recent years due to their di&ersity, en&ironmentally friendly nature, possibility of large8scale production, selecti&ity, performance under e!treme conditions, and potential applications in en&ironmental protection. [14][12]'ew of the popular e!amples of microbial
[1I]

biosurfactants

includes

Emulsan

produced

by Acinetobacter calcoaceticus, tocandida and starmerella aeruginosa

[,1]

Sophorolipids produced by se&eral yeasts belonging by Pseudomonas

clade,[1J][,3] and Ahamnolipid produced

etc.

;iosurfactants enhance the emulsification of hydrocarbons, ha&e the potential to solubilise hydrocarbon contaminants and increase their a&ailability for microbial degradation. The use of chemicals for the treatment of a hydrocarbon polluted site may contaminate the en&ironment with their by8products, whereas biological treatment may efficiently destroy pollutants, while being biodegradable themsel&es. :ence, biosurfactant8producing microorganisms may play an important role in the accelerated bioremediation of hydrocarbon8contaminated sites.[,,][,5][,7] These compounds can also be used in enhanced oil reco&ery and may be considered for other potential applications in en&ironmental protection.
[,7][,/]

0ther applications include herbicides and pesticides formulations, detergents,

healthcare and cosmetics, pulp and paper, coal, te!tiles, ceramic processing and food industries, uranium ore8processing, and mechanical dewatering of peat.[14][12][,4] Se&eral microorganisms are +nown to synthesise surface8acti&e agentsD most of them are bacteria and yeasts.[,2][,I] .hen grown on hydrocarbon substrate as the carbon source, these microorganisms synthesise a wide range of chemicals with surface acti&ity, such as glycolipid, phospholipid, and others.[,J][53] These chemicals are synthesised to emulsify the hydrocarbon substrate and facilitate its transport into the cells. n some bacterial species

such as Pseudomonas aeruginosa, biosurfactants are also in&ol&ed in a group motility beha&ior called swarming motility.

Safety and en#ironmental ris!s

"ost anionic and nonionic surfactants are nonto!ic, ha&ing %9/3 comparable to sodium chloride. The situation for cationic surfactants is more di&erse. 9ial+yldimethylammonium chlorides ha&e &ery low %9/3>s (/ g-+g) but al+ylben1yldimethylammonium chloride has an %9/3 of 3.5/ g-+g. ?rolonged e!posure of s+in to surfactants can cause chaffing because surfactants (e.g., soap) disrupts the lipid coating that protects s+in (and other) cells.[5]

$iosurfactants and Deepwater "orizon

The use of biosurfactants as a way to remo&e petroleum from contaminated sites has been studied and found to be safe and effecti&e in the remo&al petroleum products from soil. ;iosurfactants were not used by ;? after the 9eepwater :ori1on oil spill. :owe&er, unprecedented amounts of Bore!it (acti&e ingredientC Tween8I3), were sprayed directly into the ocean at the lea+ and on the sea8water>s surface, the theory being that the surfactants isolate droplets of oil, ma+ing it easier for petroleum8consuming microbes to digest the oil.