Linear Alkylbenzene Sulfonate
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Alkylbenzene sulfonates are a class of
anionic surfactant Surfactants are chemical compounds that decrease the surface tension or interfacial tension between two liquids, a liquid and a gas, or a liquid and a solid. The word ''surfactant'' is a Blend word, blend of "surface-active agent", coined in ...
s, consisting of a
hydrophilic A hydrophile is a molecule or other molecular entity that is attracted to water molecules and tends to be dissolved by water.Liddell, H.G. & Scott, R. (1940). ''A Greek-English Lexicon'' Oxford: Clarendon Press. In contrast, hydrophobes are n ...
sulfonate In organosulfur chemistry, a sulfonate is a salt, anion or ester of a sulfonic acid. Its formula is , containing the functional group , where R is typically an organyl group, amino group or a halogen atom. Sulfonates are the conjugate bases of ...
head-group and a
hydrophobic In chemistry, hydrophobicity is the chemical property of a molecule (called a hydrophobe) that is seemingly repelled from a mass of water. In contrast, hydrophiles are attracted to water. Hydrophobic molecules tend to be nonpolar and, thu ...
alkylbenzene tail-group. Along with sodium laureth sulfate, they are one of the oldest and most widely used synthetic detergents and may be found in numerous personal-care products (soaps, shampoos, toothpaste etc.) and household-care products (laundry detergent, dishwashing liquid, spray cleaner etc.).Kurt Kosswig,"Surfactants" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, 2005, Weinheim. They were introduced in the 1930s in the form of branched alkylbenzene sulfonates (BAS). However following environmental concerns these were replaced with linear alkylbenzene sulfonates (LAS) during the 1960s. Since then production has increased significantly from about one million tons in 1980, to around 3.5 million tons in 2016, making them most produced anionic surfactant after
soap Soap is a salt (chemistry), salt of a fatty acid (sometimes other carboxylic acids) used for cleaning and lubricating products as well as other applications. In a domestic setting, soaps, specifically "toilet soaps", are surfactants usually u ...
s.


Branched alkylbenzene sulfonates

Branched alkylbenzene sulfonates (BAS) were introduced in the early 1930s and saw significant growth from the late 1940s onwards, in early literature these synthetic detergents are often abbreviated as syndets. They were prepared by the Friedel–Crafts alkylation of
benzene Benzene is an Organic compound, organic chemical compound with the Chemical formula#Molecular formula, molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar hexagonal Ring (chemistry), ring with one hyd ...
with 'propylene tetramer' (also called tetrapropylene) followed by sulfonation. Propylene tetramer being a broad term for a mixture of compounds formed by the oligomerization of
propene Propylene, also known as propene, is an unsaturated organic compound with the chemical formula . It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petroleum-like od ...
, its use gave a mixture of highly branched structures. Compared to traditional soaps, BAS offered superior tolerance to hard water and better foaming. However, the highly branched tail made it difficult to biodegrade. BAS was widely blamed for the formation of large expanses of stable foam in areas of wastewater discharge such as lakes, rivers and coastal areas ( sea foams), as well as foaming problems encountered in sewage treatment and contamination of drinking water. As such, BAS was phased out of most detergent products during the 1960s, being replaced with linear alkylbenzene sulfonates (LAS), which biodegrade much more rapidly. BAS is still important in certain agrochemical and industrial applications, where rapid biodegradability is of reduced importance. For instance, inhibiting
asphaltene Asphaltenes are molecular substances that are found in crude oil, along with resins, aromatic hydrocarbons, and saturates (i.e. saturated hydrocarbons such as alkanes). The word "asphaltene" was coined by Jean-Baptiste Boussingault in 1837 whe ...
deposition from
crude oil Petroleum, also known as crude oil or simply oil, is a naturally occurring, yellowish-black liquid chemical mixture found in geological formations, consisting mainly of hydrocarbons. The term ''petroleum'' refers both to naturally occurring u ...
.


Linear alkylbenzene sulfonates

Linear alkylbenzene sulfonates (LAS) are prepared industrially by the sulfonation of linear alkylbenzenes (LABs), which can themselves be prepared in several ways. In the most common route
benzene Benzene is an Organic compound, organic chemical compound with the Chemical formula#Molecular formula, molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar hexagonal Ring (chemistry), ring with one hyd ...
is alkylated by long chain monoalkenes (e.g. dodecene) using
hydrogen fluoride Hydrogen fluoride (fluorane) is an Inorganic chemistry, inorganic compound with chemical formula . It is a very poisonous, colorless gas or liquid that dissolves in water to yield hydrofluoric acid. It is the principal industrial source of fluori ...
as a catalyst. The purified dodecylbenzenes (and related derivatives) are then sulfonated with
sulfur trioxide Sulfur trioxide (alternative spelling sulphur trioxide) is the chemical compound with the formula SO3. It has been described as "unquestionably the most conomicallyimportant sulfur oxide". It is prepared on an industrial scale as a precursor to ...
to give the
sulfonic acid In organic chemistry, sulfonic acid (or sulphonic acid) refers to a member of the class of organosulfur compounds with the general formula , where R is an organic alkyl or aryl group and the group a sulfonyl hydroxide. As a substituent, it is kn ...
. The sulfonic acid is subsequently neutralized with
sodium hydroxide Sodium hydroxide, also known as lye and caustic soda, is an inorganic compound with the formula . It is a white solid ionic compound consisting of sodium cations and hydroxide anions . Sodium hydroxide is a highly corrosive base (chemistry), ...
. The term "linear" refers to the starting
alkene In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or at the terminal position. Terminal alkenes are also known as Alpha-olefin, α-olefins. The Internationa ...
s rather than the final product, perfectly linear addition products are not seen, in-line with
Markovnikov's rule In organic chemistry, Markovnikov's rule or Markownikoff's rule describes the outcome of some addition reactions. The rule was formulated by Russian chemist Vladimir Markovnikov in 1870. Explanation The rule states that with the addition of a ...
. Thus, the alkylation of linear alkenes, even 1-alkenes such as 1-dodecene, gives several isomers of phenyldodecane.


Structure property relationships

Under ideal conditions the cleaning power of BAS and LAS is very similar, however LAS performs slightly better in normal use conditions, due to it being less affected by hard water. Within LAS itself the detergency of the various isomers are fairly similar, however their physical properties ( Krafft point, foaming etc.) are noticeably different. In particular the Krafft point of the high 2-phenyl product (i.e. the least branched isomer) remains below 0 °C up to 25% LAS whereas the low 2-phenyl cloud point is ~15 °C. This behavior is often exploited by producers to create either clear or cloudy products.


Environmental fate

The biodegradability of alkylbenzene sulfonates has been well studied, and is affected by
isomerization In chemistry, isomerization or isomerisation is the process in which a molecule, polyatomic ion or molecular fragment is transformed into an isomer with a different chemical structure. Enolization is an example of isomerization, as is tautomer ...
, in this case, branching. The salt of the linear material has an of 2.3 mg/liter for fish, about four times more toxic than the branched compound; however the linear compound biodegrades far more quickly, making it the safer choice over time. It is biodegraded rapidly under aerobic conditions with a
half-life Half-life is a mathematical and scientific description of exponential or gradual decay. Half-life, half life or halflife may also refer to: Film * Half-Life (film), ''Half-Life'' (film), a 2008 independent film by Jennifer Phang * ''Half Life: ...
of approximately 1–3 weeks; oxidative degradation initiates at the alkyl chain. Under anaerobic conditions it degrades very slowly or not at all, causing it to exist in high concentrations in
sewage sludge Sewage sludge is the residual, semi-solid material that is produced as a by-product during sewage treatment of industrial or municipal wastewater. The term "septage" also refers to sludge from simple wastewater treatment but is connected to si ...
, but this is not thought to be a cause for concern as it will rapidly degrade once returned to an oxygenated environment.


References

{{Xenobiotic-sensing receptor modulators Organic sodium salts Cleaning product components Anionic surfactants Sulfonates Glycine receptor agonists Alkyl-substituted benzenes