Surfactants are compounds that lower the surface tension (or interfacial tension) between two liquids, between a gas and a liquid, or between a liquid and a solid. Surfactants may act as detergents, wetting agents, emulsifiers, foaming agents, and dispersants.
The word surfactant is a blend of surface-active agent. Agents that increase surface tension are surface active in the literal sense but are not called surfactants since their effect is opposite to the common meaning. A common example is salting out, by adding an inorganic salt to an aqueous solution of a weakly polar substance, the substance will precipitate. The substance may itself be a surfactant, and it is one of the reasons why many surfactants are ineffective in sea water.
Composition and structureEdit
Surfactants are usually organic compounds that are amphiphilic, meaning they contain both hydrophobic groups (their tails) and hydrophilic 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 mixed with oil. The water-insoluble hydrophobic group may extend out of the bulk water phase, into the air or into the oil phase, while the water-soluble head group remains in the water phase.
World production of surfactants is estimated at 15 million tons per year, of which about half are soaps. Other surfactants produced on a particularly large scale are linear alkylbenzene sulfonates (1.7 million tons/y), lignin sulfonates (600,000 tons/y), fatty alcohol ethoxylates (700,000 tons/y), and alkylphenol ethoxylates (500,000 tons/y).
Structure of surfactant phases in waterEdit
In the bulk 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. Other types of aggregates can also be formed, such as spherical or cylindrical micelles or lipid bilayers. The shape of the aggregates depends on the chemical structure of the surfactants, namely the balance in size between the hydrophilic head and hydrophobic tail. A measure of this is the hydrophilic-lipophilic balance (HLB). Surfactants reduce the surface tension of water by adsorbing at the liquid-air interface. The relation that links the surface tension and the surface excess is known as the Gibbs isotherm.
Dynamics of surfactants at interfacesEdit
The dynamics of surfactant adsorption is of great importance for practical applications such as in foaming, emulsifying or coating processes, where bubbles or drops are rapidly generated and need to be stabilized. The dynamics of absorption depend on the diffusion coefficient of the surfactant. As the interface is created, the adsorption is limited by the diffusion of the surfactant to the interface. In some cases, there can exist an energetic barrier to adsorption or desorption of the surfactant. If such a barrier limits the adsorption rate, the dynamics are said to be ‘kinetically limited'. Such energy barriers can be due to steric or electrostatic repulsions. The surface rheology of surfactant layers, including the elasticity and viscosity of the layer, play an important role in the stability of foams and emulsions.
Characterization of interfaces and surfactant layersEdit
Interfacial and surface tension can be characterized by classical methods such as the -pendant or spinning drop method. Dynamic surface tensions, i.e. surface tension as a function of time, can be obtained by the maximum bubble pressure apparatus
Surface rheology can be characterized by the oscillating drop method or shear surface rheometers such as double-cone, double-ring or magnetic rod shear surface rheometer.
Surfactants in biologyEdit
The human body produces diverse surfactants. Pulmonary surfactant is produced in the lungs in order to facilitate breathing by increasing total lung capacity, and lung compliance. In respiratory distress syndrome or RDS, surfactant replacement therapy helps patients have normal respiration by using pharmaceutical forms of the surfactants. One example of pharmaceutical pulmonary surfactants is Survanta (beractant) or its generic form Beraksurf produced by Abbvie and Tekzima respectively. Bile salts, a surfactant produced in the liver, play an important role in digestion.
Safety and environmental risksEdit
Most anionic and non-ionic surfactants are non-toxic, having LD50 comparable to sodium chloride. The toxicity of quaternary ammonium compounds, which are antibacterial and antifungal, varies. Dialkyldimethylammonium chlorides (DDAC, DSDMAC) used as fabric softeners have low LD50 (5 g/kg) and are essentially non-toxic, while the disinfectant alkylbenzyldimethylammonium chloride has an LD50 of 0.35 g/kg. Prolonged exposure to surfactants can irritate and damage the skin because surfactants disrupt the lipid membrane that protects skin and other cells. Skin irritancy generally increases in the series non-ionic, amphoteric, anionic, cationic surfactants.
Anionic surfactants can be found in soils as the result of sewage sludge application, wastewater irrigation, and remediation processes. Relatively high concentrations of surfactants together with multimetals can represent an environmental risk. At low concentrations, surfactant application is unlikely to have a significant effect on trace metal mobility.
In the case of the Deepwater Horizon oil spill, unprecedented amounts of Corexit were sprayed directly into the ocean at the leak and on the sea-water's surface. The apparent theory being that the surfactants isolate droplets of oil, making it easier for petroleum-consuming microbes to digest the oil. The active ingredient in Corexit is dioctyl sodium sulfosuccinate (DOSS), sorbitan monooleate (Span 80), and polyoxyethylenated sorbitan monooleate (Tween-80).
Because of the volume of surfactants released into the environment, their biodegradation is of great interest. Strategies to enhance degradation include ozone treatment and biodegradation. Two major surfactants, linear alkylbenzene sulfonates (LAS) and the alkyl phenol ethoxylates (APE) break down under aerobic conditions found in sewage treatment plants and in soil to nonylphenol, which is thought to be an endocrine disruptor. Interest in biodegradable surfactants has led to much interest in "biosurfactants" such as those derived from amino acids.
The annual global production of surfactants was 13 million tonnes in 2008. In 2014, the world market for surfactants reached a volume of more than US$33 billion. Market researchers expect annual revenues to increase by 2.5% per year to around $40.4 billion until 2022. The commercially most significant type of surfactants is currently the anionic surfactant LAS, which is widely used in cleaners and detergents.
Surfactants play an important role as cleaning, wetting, dispersing, emulsifying, foaming and anti-foaming agents in many practical applications and products, including detergents, fabric softeners, motor oils, emulsions, soaps, paints, adhesives, inks, anti-fogs, ski waxes, snowboard wax, deinking of recycled papers, in flotation, washing and enzymatic processes, and laxatives. Also agrochemical formulations such as herbicides (some), insecticides, biocides (sanitizers), and spermicides (nonoxynol-9). Personal care products such as cosmetics, shampoos, shower gel, hair conditioners, and toothpastes. Surfactants are used in firefighting and pipelines (liquid drag reducing agents). Alkali surfactant polymers are used to mobilize oil in oil wells.
The displacement of air from the matrix of cotton pads and bandages so that medicinal solutions can be absorbed for application to various body areas; the displacement of dirt and debris by the use of detergents in the washing of wounds; and the application of medicinal lotions and sprays to surface of skin and mucous membranes.
Detergents in biochemistry and biotechnologyEdit
In solution, detergents help solubilize a variety of chemical species by dissociating aggregates and unfolding proteins. Popular surfactants in the biochemistry laboratory are sodium lauryl sulfate (SDS) and cetyl trimethylammonium bromide (CTAB). Detergents are key reagents to extract protein by lysis of the cells and tissues: They disorganize the membrane's lipid bilayer (SDS, Triton X-100, X-114, CHAPS, DOC, and NP-40), and solubilize proteins. Milder detergents such as octyl thioglucoside, octyl glucoside or dodecyl maltoside are used to solubilize membrane proteins such as enzymes and receptors without denaturing them. Non-solubilized material is harvested by centrifugation or other means. For electrophoresis, for example, proteins are classically treated with SDS to denature the native tertiary and quaternary structures, allowing the separation of proteins according to their molecular weight.
Detergents have also been used to decellularise organs. This process maintains a matrix of proteins that preserves the structure of the organ and often the microvascular network. The process has been successfully used to prepare organs such as the liver and heart for transplant in rats. Pulmonary surfactants are also naturally secreted by type II cells of the lung alveoli in mammals.
Quantum dot preparationEdit
Surfactants are used with quantum dots in order to manipulate the growth, assembly, and electrical properties of quantum dots, in addition to mediating reactions on their surfaces. Research is ongoing in how surfactants arrange on the surface of the quantum dots.
Surfactants in droplet-based microfluidicsEdit
The "tails" of most surfactants are fairly similar, consisting of a hydrocarbon chain, which can be branched, linear, or aromatic. Fluorosurfactants have fluorocarbon chains. Siloxane surfactants have siloxane chains.
Many important surfactants include a polyether chain terminating in a highly polar anionic group. The polyether groups often comprise ethoxylated (polyethylene oxide-like) sequences inserted to increase the hydrophilic character of a surfactant. Polypropylene oxides conversely, may be inserted to increase the lipophilic character of a surfactant.
Surfactant molecules have either one tail or two; those with two tails are said to be double-chained.
Most commonly, surfactants are classified according to polar head group. A non-ionic surfactant has no charged groups in its head. The head of an ionic surfactant carries a net positive, or negative charge. If the charge is negative, the surfactant is more specifically called anionic; if the charge is positive, it is called cationic. If a surfactant contains a head with two oppositely charged groups, it is termed zwitterionic. Commonly encountered surfactants of each type include:
Anionic: sulfate, sulfonate, and phosphate, carboxylate derivativesEdit
Anionic surfactants contain anionic functional groups at their head, such as sulfate, sulfonate, phosphate, and carboxylates. Prominent alkyl sulfates include ammonium lauryl sulfate, sodium lauryl sulfate (sodium dodecyl sulfate, SLS, or SDS), and the related alkyl-ether sulfates sodium laureth sulfate (sodium lauryl ether sulfate or SLES), and sodium myreth sulfate.
- Docusate (dioctyl sodium sulfosuccinate)
- Perfluorooctanesulfonate (PFOS)
- Alkyl-aryl ether phosphates
- Alkyl ether phosphates
Carboxylates are the most common surfactants and comprise the carboxylate salts (soaps), such as sodium stearate. More specialized species include sodium lauroyl sarcosinate and carboxylate-based fluorosurfactants such as perfluorononanoate, perfluorooctanoate (PFOA or PFO).
Cationic head groupsEdit
Permanently charged quaternary ammonium salts: cetrimonium bromide (CTAB), cetylpyridinium chloride (CPC), benzalkonium chloride (BAC), benzethonium chloride (BZT), dimethyldioctadecylammonium chloride, and dioctadecyldimethylammonium bromide (DODAB).
Zwitterionic (amphoteric) surfactants have 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 variable and include sulfonates, as in the sultaines CHAPS (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate) and cocamidopropyl hydroxysultaine. Betaines such as cocamidopropyl betaine have a carboxylate with the ammonium. The most common biological zwitterionic surfactants have a phosphate anion with an amine or ammonium, such as the phospholipids phosphatidylserine, phosphatidylethanolamine, phosphatidylcholine, and sphingomyelins.
Non-ionic surfactants have covalently bonded oxygen-containing hydrophilic groups, which are bonded to hydrophobic parent structures. The water-solubility of the oxygen groups is the result of hydrogen bonding. Hydrogen bonding decreases with increasing temperature, and the water solubility of non-ionic surfactants therefore decreases with increasing temperature.
Non-ionic surfactants are less sensitive to water hardness than anionic surfactants, and they foam less strongly. The differences between the individual types of non-ionic surfactants are slight, and the choice is primarily governed having regard to the costs of special properties (e.g., effectiveness and efficiency, toxicity, dermatological compatibility, biodegradability) or permission for use in food.
Fatty alcohol ethoxylatesEdit
- Narrow-range ethoxylate
- Octaethylene glycol monododecyl ether
- Pentaethylene glycol monododecyl ether
Alkylphenol ethoxylates (APEs or APEOs)Edit
Fatty acid ethoxylatesEdit
Fatty acid ethoxylates are a class of very versatile surfactants, which combine in a single molecule the characteristic of a weakly anionic, pH-responsive head group with the presence of stabilizing and temperature responsive ethyleneoxide units.
Special ethoxylated fatty esters and oilsEdit
Ethoxylated amines and/or fatty acid amidesEdit
Terminally blocked ethoxylatesEdit
Fatty acid esters of polyhydroxy compoundsEdit
Fatty acid esters of glycerolEdit
Fatty acid esters of sorbitolEdit
Fatty acid esters of sucroseEdit
- Anti-fog – Chemicals that prevent the condensation of water as small droplets on a surface
- Cleavable detergent
- Emulsion – Mixture of two or more liquids that are generally immiscible
- MBAS assay, an assay that indicates anionic surfactants in water with a bluing reaction.
- Oil dispersants
- Surfactants in paint
- Rosen MJ, Kunjappu JT (2012). Surfactants and Interfacial Phenomena (4th ed.). Hoboken, New Jersey: John Wiley & Sons. p. 1. ISBN 978-1-118-22902-6. Archived from the original on 8 January 2017.
- "Bubbles, Bubbles, Everywhere, But Not a Drop to Drink". The Lipid Chronicles. 11 November 2011. Archived from the original on 26 April 2012. Retrieved 1 August 2012.
- Kurt Kosswig "Surfactants" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, 2005, Weinheim. doi:10.1002/14356007.a25_747
- Maldonado-Valderrama, Julia; Wilde, Pete; MacIerzanka, Adam; MacKie, Alan (2011). "The role of bile salts in digestion". Advances in Colloid and Interface Science. 165 (1): 36–46. doi:10.1016/j.cis.2010.12.002. PMID 21236400.
- Metcalfe TL, Dillon PJ, Metcalfe CD (April 2008). "Detecting the transport of toxic pesticides from golf courses into watersheds in the Precambrian Shield region of Ontario, Canada". Environ. Toxicol. Chem. 27 (4): 811–8. doi:10.1897/07-216.1. PMID 18333674.
- Emmanuel E, Hanna K, Bazin C, Keck G, Clément B, Perrodin Y (April 2005). "Fate of glutaraldehyde in hospital wastewater and combined effects of glutaraldehyde and surfactants on aquatic organisms". Environ Int. 31 (3): 399–406. doi:10.1016/j.envint.2004.08.011. PMID 15734192.
- Murphy MG, Al-Khalidi M, Crocker JF, Lee SH, O'Regan P, Acott PD (April 2005). "Two formulations of the industrial surfactant, Toximul, differentially reduce mouse weight gain and hepatic glycogen in vivo during early development: effects of exposure to Influenza B Virus". Chemosphere. 59 (2): 235–46. Bibcode:2005Chmsp..59..235M. doi:10.1016/j.chemosphere.2004.11.084. PMID 15722095.
- Hernández-Soriano Mdel C, Degryse F, Smolders E (March 2011). "Mechanisms of enhanced mobilisation of trace metals by anionic surfactants in soil". Environ. Pollut. 159 (3): 809–16. doi:10.1016/j.envpol.2010.11.009. PMID 21163562.
- Hernández-Soriano Mdel C, Peña A, Dolores Mingorance M (2010). "Release of metals from metal-amended soil treated with a sulfosuccinamate surfactant: effects of surfactant concentration, soil/solution ratio, and pH". J. Environ. Qual. 39 (4): 1298–305. doi:10.2134/jeq2009.0242. PMID 20830918.
- "European Maritime Safety Agency. Manual on the Applicability of Oil Dispersants; Version 2; 2009". Archived from the original on 5 July 2011. Retrieved 19 May 2017.
- Committee on Effectiveness of Oil Spill Dispersants (National Research Council Marine Board) (1989). "Using Oil Spill Dispersants on the Sea". National Academies Press. Retrieved 31 October 2015.
- Rebello, Sharrel; Asok, Aju K.; Mundayoor, Sathish; Jisha, M. S. (2014). "Surfactants: Toxicity, remediation and green surfactants". Environmental Chemistry Letters. 12 (2): 275–287. doi:10.1007/s10311-014-0466-2.
- Ying, Guang-Guo (2006). "Fate, behavior and effects of surfactants and their degradation products in the environment". Environment International. 32 (3): 417–431. doi:10.1016/j.envint.2005.07.004. PMID 16125241.
- Mergel, Maria. "Nonylphenol and Nonylphenol Ethoxylates." Toxipedia.org. N.p., 1 Nov. 2011. Web. 27 Apr. 2014.
- Scott MJ, Jones MN (November 2000). "The biodegradation of surfactants in the environment". Biochim. Biophys. Acta. 1508 (1–2): 235–51. doi:10.1016/S0304-4157(00)00013-7. PMID 11090828.
- Reznik GO, Vishwanath P, Pynn MA, Sitnik JM, Todd JJ, Wu J, et al. (May 2010). "Use of sustainable chemistry to produce an acyl amino acid surfactant". Appl. Microbiol. Biotechnol. 86 (5): 1387–97. doi:10.1007/s00253-009-2431-8. PMID 20094712.
- USEPA: "2010/15 PFOA Stewardship Program" Archived 27 October 2008 at the Wayback Machine Accessed October 26, 2008.
- "Market Report: World Surfactant Market". Acmite Market Intelligence. Archived from the original on 13 September 2010.
- Market Study on Surfactants (2nd edition, April 2015), by Ceresana Research Archived 20 March 2012 at the Wayback Machine
- Paria, Santanu (2008). "Surfactant-enhanced remediation of organic contaminated soil and water". Advances in Colloid and Interface Science. 138 (1): 24–58. doi:10.1016/j.cis.2007.11.001. PMID 18154747.
- Percival, S.l.; Mayer, D.; Malone, M.; Swanson, T; Gibson, D.; Schultz, G. (2 November 2017). "Surfactants and their role in wound cleansing and biofilm management". Journal of Wound Care. 26 (11): 680–690. doi:10.12968/jowc.2017.26.11.680. ISSN 0969-0700. PMID 29131752.
- Mc Callion, O. N. M.; Taylor, K. M. G.; Thomas, M.; Taylor, A. J. (8 March 1996). "The influence of surface tension on aerosols produced by medical nebulisers". International Journal of Pharmaceutics. 129 (1): 123–136. doi:10.1016/0378-5173(95)04279-2. ISSN 0378-5173.
- Wein, Harrison (28 June 2010). "Progress Toward an Artificial Liver Transplant – NIH Research Matters". National Institutes of Health (NIH). Archived from the original on 5 August 2012.
- Murray, C. B.; Kagan, C. R.; Bawendi, M. G. (2000). "Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies". Annual Review of Materials Research. 30 (1): 545–610. Bibcode:2000AnRMS..30..545M. doi:10.1146/annurev.matsci.30.1.545.
- Zherebetskyy D, Scheele M, Zhang Y, Bronstein N, Thompson C, Britt D, Salmeron M, Alivisatos P, Wang LW (June 2014). "Hydroxylation of the surface of PbS nanocrystals passivated with oleic acid". Science. 344 (6190): 1380–4. Bibcode:2014Sci...344.1380Z. doi:10.1126/science.1252727. PMID 24876347.
- Baret, Jean-Christophe (10 January 2012). "Surfactants in droplet-based microfluidics". Lab on a Chip. 12 (3): 422–433. doi:10.1039/C1LC20582J. ISSN 1473-0189.
- Reich, Hans J. (2012). "Bordwell pKa Table (Acidity in DMSO)". University of Wisconsin.
- Chiappisi, Leonardo (December 2017). "Polyoxyethylene alkyl ether carboxylic acids: An overview of a neglected class of surfactants with multiresponsive properties". Advances in Colloid and Interface Science. 250: 79–94. doi:10.1016/j.cis.2017.10.001. PMID 29056232.
- Media related to Surfactants at Wikimedia Commons