DETERGENTS

Introduction: Synthetic detergents have similar molecular structures and properties as soap. Although the cleansing action is similar, the detergents do not react as readily with hard water ions of calcium and magnesium. There are over a thousand synthetic detergents available in the United States. Detergent molecular structures consist of a long hydrocarbon chain and a water soluble ionic group. Most detergents have a negative ionic group and are called anionic detergents. The majority are alky sulfates. Others are "surfactants" (from surface active agents) which are generally known as alkyl benzene sulfonates.

Neutral or non-ionic detergents:

Nonionic detergents are used in dish washing liquids. Since the detergent does not have any ionic groups, it does not react with hard water ions. In addition, nonionic detergents foam less than ionic detergents. The detergent molecules must have some polar parts to provide the necessary water solubility. In the graphic on the left, the polar part of the molecule consists of three alcohol groups and an ester group. The non-polar part is the usual long hydrocarbon chain.

Bile Salts - Intestinal Natural Detergents: Bile acids are produced in the liver and secreted in the intestine via the gall bladder. Bile acids are oxidation products of cholesterol. First the cholesterol is converted to the trihydroxy derivative containing three alcohol groups. The end of the alkane chain at C # 17 is converted into an acid, and finally the amino acid, glycine is bonded through an amide bond. The acid group on the glycine is converted to a salt. The bile salt is called sodiumglycoholate. Another salt can be made with a chemical called taurine. The main function of bile salts is to act as a soap or detergent in the digestive processes. The major action of a bile salt is to emulsify fats and oils into smaller droplets. The various enzymes can then break down the fats and oils. QUES. Explain how bile salts work to emulsify fats. Talk about the polar and non-polar parts of the molecule.

A detergent is a surfactant or a mixture of surfactants with "cleaning properties in dilute solutions."[1] In common usage, "detergent" refers to alkylbenzenesulfonates, a family of compounds that are similar to soap but are less affected by hard water. In most household contexts, the term detergent by itself refers specifically to laundry detergent or dish detergent, as opposed to hand soap or other types of cleaning agents. Detergents are commonly available as powders or concentrated solutions. Detergents work because they are amphiphilic - partly hydrophilic (polar) and partly hydrophobic (non-polar). Their dual nature facilitates the mixture of hydrophobic compounds (like oil and grease) with water. Because air is not hydrophillic, detergents are also foaming agents to varying degrees. Completely non-polar solvents known as degreasers can also remove hydrophobic contaminants but may not dissolve in water because of a lack of polar elements.

Chemical classification of detergents

Detergents are classified into three broad groupings, depending on the electrical charge of the surfactants.

Anionic detergents
Typical anionic detergents are alkylbenzenesulfonates. The alkylbenzene portion of these anions is lipophilic and the sulfonate is hydrophilic. Two varieties have been popularized, those with

branched alkyl groups and those with linear alkyl groups. The former were largely phased out in economically advanced societies because they are poorly biodegradable.[2] An estimated 6 billion kilograms of anionic detergents are produced annually for domestic markets. Bile acids, such as deoxycholic acid (DOC), are anionic detergents produced by the liver to aid in digestion and absorption of fats and oils.

Three kinds of anionic detergents: a branched sodium dodecylbenzenesulfonate, linear sodium dodecylbenzenesulfonate, and a soap.

Cationic detergents
Cationic detergents are similar to the anionic ones, with a hydrophobic component, but, instead of the anionic sulfonate group, the cationic surfactants have quaternary ammonium as the polar end. The ammonium center is positively charged.[2]

Non-ionic and zwitterionic detergents

Non-ionic detergents are characterized by their uncharged, hydrophilic headgroups. Typical nonionic detergents are based on polyoxyethylene or a glycoside. Common examples of the former include Tween, Triton, and the Brij series. These materials are also known as ethoxylates or PEGylates). Glycosides have a sugar as their uncharged hydrophilic headgroup. Examples include octyl-thioglucoside and maltosides. HEGA and MEGA series detergents are similar, possessing a sugar alcohol as headgroup. Zwitterionic detergents possess a net zero charge arising from the presence of equal numbers of +1 and -1 charged chemical groups. Examples include CHAPS. See surfactants for more applications.

Major applications of detergents

Laundry detergents
One of the largest applications of detergents is for cleaning clothing. The formulations are complex, reflecting the diverse demands of the application and the highly competitive consumer market. In general, laundry detergents contain water softeners, surfactants, bleach, enzymes, brighteners, fragrances, and many other agents. The formulation is strongly affected by the temperature of the cleaning water and varies from country to country.

Fuel additives
Both carburetors and fuel injector components of Otto engines benefit from detergents in the fuels to prevent fouling. Concentrations are about 300 ppm. Typical detergents are long-chain amines and amides such as polyisobuteneamine and polyisobuteneamide/succinimide.[3]

Soapless soap
Soapless soap refers to a soapfree liquid cleanser with a slightly acidic pH.[4] Soapless soaps are used in an array of products. Laundry detergent, or washing powder, is a substance that is a type of detergent (cleaning agent) that is added for cleaning laundry. In common usage, "detergent" refers to mixtures of chemical compounds including alkylbenzenesulfonates, which are similar to soap but are less affected by "hard water." In most household contexts, the term detergent refers to laundry detergent vs hand soap or other types of cleaning agents. Most detergent is delivered in powdered form.[1]

History
From ancient times, chemical additives were recognized for their ability to facilitate the mechanical washing with water. The Italians used a mix of sulfur and water with charcoal to clean cloth. Egyptians added ashes and silicates to soften water. Soaps were the first detergents.
[2]

The detergent effects of certain synthetic surfactants were noted in Germany in 1917, in

response to shortages of soap during World War I. In the 1930s, commercially viable routes to

fatty alcohols were developed, and these new materials were converted to their sulfate esters, key ingredients in the commercially important German brand FEWA, produced by BASF, and Dreft, the US brand produced by Procter and Gamble. Such detergents were mainly used in industry until after World War II. By then, new developments and the later conversion of aviation fuel plants to produce tetrapropylene, used in household detergents, caused a fast growth of domestic use in the late 1940s.[3] The use of enzymes for laundry was introduced in the early part of the 1900s by Otto Rohm. Only in the latter part of the century with the availability of thermally robust bacterial enzymes did this technology become mainstream.[4] At the present time, soap has largely been displaced as the main cleaning agent in developed countries. Soap is, by weight, relatively ineffective, and it is highly sensitive to deactivation by hard water. By the 1950s, soap had almost been completely replaced by branched alkylbenzenesulfonates, but these detergents were found to be poorly biodegradable. Linear alkylbenzenesulfonates (LABs), however, proved to be both highly effective in cleaning and more biodegradable than the branched relatives. LABs remain the main detergents used domestically. Other detergents that have been developed include the linear alkylsulfonates and olefinsulfonates, which also resist deactivation by hard water. Both remain specialty products, for example only an estimated 60 million kilograms of the sodium alkylsulfonates are produced annually.[5] During the early development of non-soap surfactants as commercial cleaning products, the term syndet, short for synthetic detergent, was promoted to indicate the distinction from so-called natural soaps.

Chemistry of detergents
Many kinds of molecules and ions can serve as high-efficiency surfactants. They are often classified according to the charge of the molecule or ion, the three main classes being anionic, neutral, and cationic detergents. Anionic detergents are most commonly encountered for domestic laundry detergents. Detergents are ions or molecules that contain both polar and nonpolar components. The polar component allows the detergent to dissolve in the water, whereas the nonpolar portion solubilizes greasy ("hydrophobic") materials that are the usual target of the cleaning process. An estimated 6 billion kilograms of detergents are produced annually for domestic markets.[5]

Three kinds of anionic detergents: branch alkylbenzenesulfonates, linear alkylbenzenesulfonates, and a soap.

Components
Modern detergent formulations - the entire product vs just the surfactant - contain several components. Three main ingredients are builders (50% by weight, approximately), the alkylbenzenesulfonate surfactant (15%), and bleaches (7%).[5]

Builders
Builders are water softeners. These chemical compounds are agents that remove calcium ions by complexation or precipitation. Typical builders are sodium carbonate, complexation agents, soap, and zeolites. They function by sequestering or precipitating the problematic ions. One of the most common builders is sodium triphosphate, which is used on very large scale for this application.

Bleach
The main targets of bleaches are of vegetable origin and include chlorophyll, anthocyanin dyes, tannins, humic acids, and carotenoid pigments. Most bleaches in laundry detergents are oxidizers, e.g., sodium perborate or sodium hypochlorite, In addition, other agents are added as "bleach activators", to enhance the effectiveness of the bleaching agent; a popular one is tetraacetylethylenediamine.

Enzymes

Many laundry detergents contain enzymes. The amounts of enzyme can be up to about 2% by weight of the product. These agents are required to degrade recalcitrant stains composed of proteins, fats, or carbohydrates. Each type of stain requires a different type of enzyme, i.e., protease for proteins, lipases for greases, and amylases for carbohydrates.

Other ingredients
Many other ingredients are added depending on the specific application. Such additives modify the foaming properties of the product by either stabilizing or counteracting foam. Other ingredients increase or decrease the viscosity of the solution, or solubilize other ingredients. Corrosion inhibitors counteract damage to washing equipment. "Dye transfer inhibitors" prevent dyes from one article from colouring other items. "Antiredeposition agents" are used to prevent fine soil particles from reattaching to the product being cleaned. Carboxymethyl cellulose is used for this purpose.[5] A number of ingredients affect aesthetic properties of the item to be cleaned or the detergent itself before or during use. These agents include optical brighteners, fabric softeners, and colourants. A variety of perfumes are also components of modern detergents, provided that they are compatible with the other components and do not affect the colour of the cleaned item. The perfumes are typically a mixture of many compounds, a popular component being cyclohexyl salicylate, which is related to oil of wintergreen.[5]

Environmental concerns
Early in the introduction of sulfonate-based detergents, concerns were voiced over the low rates of biodegradation of the branched alkylbenzenesulfonates. This problem was addressed by the introduction of linear alkylbenzenesulfonates.[6] A more profound problem arises from the heavy use of sodium triphosphate, which can comprise up to 50% by weight of detergents. The discharge of soluble phosphates into natural waters has led to problem with eutrophication of lakes and streams. The replacement of sodium triphosphate by zeolites offers some relief to this problem.[5] With respect to the phosphate additives, between 1940 and 1970 "the amount of phosphates in city wastewater increased from 20,000 to 150,000 tons per year."[7] With the increase in phosphates, algal blooms grew

splendidly on the excess phosphorus and consumed most of the oxygen in the waters, killing fish and plants.[7] In 2004, the European Union introduced regulations to require biodegradability in all detergents,
[8]

and intends to ban phosphates in domestic products from 2013.[9]

Australia began phasing out the use of phosphates in its detergents in 2011, with an all-out ban expected to take effect in 2014.[10] Pursuant to findings published in 2006 by the Shenkar College of Engineering and Design indicating that liquid detergents are "much more environment-friendly" than powdered detergents, Israel's Ministry of the Environment began recommending that consumers prefer liquid detergent over powdered ones "for laundry which is not heavily stained."[11]

Cleavable detergent
Cleavable detergents, also known as cleavable surfactants, are special surfactants (detergents) that are used in biochemistry and especially in proteomics to enhance protein denaturation and solubility. The detergent is rendered inactive by cleavage, usually under acidic conditions, in order to make the sample compatible with a following procedure or in order to selectively remove the cleavage products. Applications for cleavable detergents include protease digestion of proteins such as in-gel digestion with trypsin after SDS PAGE and peptide extractions from electrophoresis gels. Cleavable detergents are mainly used in sample preparations for mass spectrometry.

PPS
PPS, available as PPS Silent Surfactant from Protein Discovery, is the abbreviation for sodium 3-(4-(1,1-bis(hexyloxy)ethyl)pyridinium-1-yl)propane-1-sulfonate. This acetalic detergent is split under acidic conditions
[1][2]

into

hexanol

and

the

zwitterionic

3-acetyl-1-(3-

sulfopropyl)pyridinium.

ProteaseMAX
ProteaseMAX is the brandname of Promega for sodium 3-((1-(furan-2yl)undecyloxy)carbonylamino)propane-1-sulfonate. This cleavable detergent is sensitive to heat and acid and is degraded during a typical trypsin digestion into the uncharged lipophilic compound 1-(furan-2-yl)undecan-1-ol and the zwitterionic 3-aminopropane-1-sulfonic acid (homotaurine), which can be removed by C18 solid phase extraction during sample work-up.[3][4]

RapiGest SF
RapiGest SF is an acid-cleavable anionic detergent marketed by Waters Corporation.[5] No information about its chemical structure has been published.

Others
MALDI matrix compounds such as -cyano-4-hydroxycinnamic acid have been linked through a linker consisting of an unsymmetric formaldehyde acetals to dodecanol. This type of cleavable detergent is inherently compatible with MALDI and does not have to be removed prior to analysis[6]:

UV light- or fluoride-cleavable surfactants have also been developed but are not in current use.[6]

How Do Detergents Clean?

Detergents and soaps are used for cleaning because pure water can't remove oily, organic soiling. Soap cleans by acting as an emulsifier. Basically, soap allows oil and water to mix so that oily grime can be removed during rinsing. Detergents were developed in response to the shortage of the animal and vegetable fats used to make soap during World War I and World War II. Detergents are primarily surfactants, which could be produced easily from petrochemicals. Surfactants lower the surface tension of water, essentially making it 'wetter' so that it is less likely to stick to itself and more likely to interact with oil and grease. Modern detergents contain more than surfactants. Cleaning products may also contain enzymes to degrade protein-based stains, bleaches to de-color stains and add power to cleaning agents, and blue dyes to counter yellowing. Like soaps, detergents have hydrophobic or water-hating molecular chains and hydrophilic or water-loving components. The hydrophobic hydrocarbons are repelled by water, but are attracted to oil and grease. The hydrophilic end of the same molecule means that one end of the molecule will be attracted to water, while the other side is binding to oil. Neither detergents nor soap accomplish anything except binding to the soil until some mechanical energy or agitation is added into the equation. Swishing the soapy water around allows the soap or detergent to pull the grime away from clothes or dishes and into the larger pool of rinse water. Rinsing washes the detergent and soil away. Warm or hot water melts fats and oils so that it is easier for the soap or detergent to dissolve the soil and pull it away into the rinse water. Detergents are similar to soap, but they are less likely to form films (soap scum) and are not as affected by the presence of minerals in water (hard water). Modern detergents may be made from petrochemicals or from oleochemicals derived from plants and animals. Alkalis and oxidizing agents are also chemicals found in detergents. Here's a look at the functions these molecules serve:

Petrochemicals/Oleochemicals These fats and oils are hydrocarbon chains which are attracted to the oily and greasy grime.

Oxidizers Sulfur trioxide, ethylene oxide, and sulfuric acid are among the molecules used to produce the hydrophilic component of surfactants. Oxidizers provide an energy source for chemical reactions. These highly reactive compounds also act as bleaches.

Alkalis Sodium and potassium hydroxide are used in detergents even as they are used in soapmaking. They provide positively charged ions to promote chemical reactions.

Conclusion:The detergents produced this way work equally well in hard, soft, acid, hot or cold water. They don t leave scum and are very powerful cleaning agents. However, the new product is so stable that it persistent in water waste and does not break down. There were problems with excessive foaming in natural and sewage waterways. The solution to this was to replace non biodegradable branched chain with a linear hydrocarbon chain. The second problem, is the phosphate additives, these are fertilizers and when released into the waterways feed plants including algae which take oxygen out of the water, killing fish and producing a bad hydrogen sulfide smell. There are now regulations on phosphate levels. The cleaning action of soap and synthetic detergents are very similar, they are both surfactants. They act as emulsifying agents and reduce the surface tension of water allowing it to wet better. Each has their own disadvantages and advantages. I think the production of synthetic detergents is a good thing especially since all the time improvements are being made to make them environmentally friendly.