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Detergents and Surfactants

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. Quiz: Whic h part of the molecule is soluble in water? Which part of the molecule is insoluble in water? Which part of the molecule is interacts with dirt or oil?

Answ er

Answ er

Answ er

Cationic Detergents: Another class of detergents have a positive ionic charge and are called "cationic" detergents. In addition to being good cleansing agents, they also possess germicidal properties which makes them useful in hospitals. Most of these detergents are derivatives of ammonia. A cationic detergent is most likely to be found in a shampoo or clothes "rinse". The purpose is to neutralize the static electrical charges from residual anionic (negative ions) detergent molecules. Since the negative charges repel each other, the positive cationic detergent neutralizes this charge. It may be surprising that it even works because the ammonium (+1) nitrogen is buried under the methyl groups as can be seen in the space filling model.

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.

Detergent Properties and Applications

By: Vicki Caligur, BioFiles 2008, 3.3, 14.

The key to detergent function is an amphipathic structure. All detergents are characterized as containing a hydrophilic head region and a hydrophobic tail region (see Figure 1).

Figure 1. Structure of the anionic detergent sodium dodecyl sulfate (SDS), showing the hydrophilic and hydrophobic regions. These structural characteristics allow detergents to aggregate in aqueous media. At a sufficiently high concentration, the polar hydrophilic region of each molecule is oriented toward the polar solute (water) while the hydrophobic regions are grouped together to form thermodynamically stable micelles with hydrophobic cores. The hydrophobic core region of the detergent micelle associates with the hydrophobic surfaces of proteins and results in soluble protein-detergent complexes. Figure 2 is a simple illustration of

a micelle to demonstrate the orientation concept. Actual micelle structures are more complex and dynamic, and can change due to detergent concentration and solution composition. 1

Figure 2. Simple illustration of a sodium dodecyl sulfate micelle. Biological detergents are commonly used to disrupt the bipolar lipid membrane of cells in order to release and solubilize membrane-bound proteins. Some detergents can be used to solubilize recombinant proteins, while others are recommended for the stabilization, crystallization, or denaturation of proteins. Detergents can align at aqueous/non-aqueous interfaces, resulting in reduced surface tension, increased miscibility, and stabilization of emulsions. Additional detergent applications include:
Extraction of DNA and RNA Solubilization of specimens for diagnostic applications Cell lysis Liposome preparation Prevention of reagent and analyte precipitation from solution Prevention of non-specific binding in immunoassays

Detergent Physical Characteristics

The concentration at which micelles begin to form is the critical micelle concentration (CMC). The CMC is the maximum monomer concentration and constitutes a measure of the free energy of micelle formation. The lower the CMC, the more stable the micelle and the more slowly molecules are incorporated into or removed from the micelle. The structure of the hydrophobic region of the detergent can affect the micelle structure. An increase in the length of the hydrophobic hydrocarbon chain of ionic

detergents results in an increased micelle size and a lower CMC, as fewer molecules are needed to construct a micelle. The average number of monomers in a micelle is the aggregation number. The CMC and aggregation number values are highly dependent on factors such as temperature, pH, ionic strength, and detergent homogeneity and purity. Slight discrepancies in reported values for CMC and aggregation number may be the result of variations in the analytical methods used to determine the values. Aggregation number values are also shifted by concentration, since the number of detergent molecules per micelle may increase if the concentration is above the CMC. Ease of removal or exchange is an important factor in the selection of a detergent. Some of the more common detergent removal methods include:
Dialysis Gel filtration chromatography Hydrophobic adsorption chromatography Protein precipitation

The CMC value associated with the detergent is a useful guide to hydrophobic binding strength. Detergents with higher CMC values have weaker binding and are subsequently easier to remove by dialysis or displacement methods. Detergents with low CMC values require less detergent in order to form micelles and solubilize proteins or lipids. Another useful parameter when evaluating detergents for downstream removal is the micelle molecular weight, which indicates relative micelle size. Smaller micelles are more easily removed and are usually desirable when protein-detergent complexes are to be separated based on the molecular size of the protein. The micelle molecular weight may be calculated by multiplying the aggregation number by the monomer molecular weight. The cloud point is the temperature at which the detergent solution near or above its CMC separates into two phases. The micelles aggregate, typically forming a cloudy phase with high detergent concentration, while the balance of the solution becomes detergent-depleted. The resulting two-phase solution can be separated, with the extracted protein being located in the detergent-rich phase. Detergents with low cloud point temperatures, such as TRITON X-114 (cloud point ~23 C) are recommended for use with proteins since high cloud point temperatures may denature solubilized proteins. The cloud point can be affected by changes in detergent concentration, temperature, and the addition of salt or polymers such as dextran and polyethylene glycol. Note that the detergent-rich phase is also contingent on the specific detergent(s) and salt concentration; under some conditions the phase may be clear rather than cloudy and be located as either the upper or lower phase of the solution. In non-ionic detergents, this behavior has been applied in the phase separation and purification of membrane proteins.2

Detergent Types and Selection

When selecting a detergent, the first consideration is usually the form of the hydrophilic group:

Anionic Cationic Non-ionic Zwitterionic (ampholytic)

Anionic and cationic detergents are considered biologically harsh detergents because they typically modify protein structure to a greater extent than neutrally charged detergents. The degree of denaturation varies with the individual protein and the particular detergent and concentration. Ionic detergents are more sensitive to pH, ionic strength, and the nature of the counter ion, and can interfere with downstream charge-based analytical methods. Non-ionic detergents are considered to be mild detergents because they are less likely th an ionic detergents to denature proteins. By not separating protein-protein bonds, non-ionic detergents allow the protein to retain its native structure and functionality, although detergents with shorter hydrophobic chain lengths are more likely to cause protein deactivation. Many nonionic detergents can be classified into three structure types:
Poly(oxyethylene) ethers and related polymers Bile salts Glycosidic detergents

Poly(oxyethylene) ethers and related detergents have a neutral, polar head and hydrophobic tails that are oxyethylene polymers (e.g. Brij and TWEEN) or ethyleneglycoether polymers (e.g. TRITON). The tertoctylphenol poly(ethyleneglycoether) series of detergents, which includes TRITON X-100 and IGEPAL CA-630, have an aromatic head that interferes with downstream UV analysis techniques. Bile salts have a steroid core structure with a polar and apolar orientation, rather than the more obvious nonpolar tail structure of other detergents. Bile salts may be less denaturing than linear chain detergents with the same polar head group. Glycosidic detergents have a carbohydrate, typically glucose or maltose, as the polar head and an alkyl chain length of 7-14 carbons as the polar tail. Zwitterionic detergents have characteristics of both ionic and non-ionic detergent types. Zwitterionic detergents are less denaturing than ionic detergents and have a net neutral charge, similar to non-ionic detergents. They are more efficient than non-ionic detergents at disrupting protein-protein bonds and reducing aggregation. These properties have been used for chromatography, mass spectrometry, and electrophoresis methods, and solubilization of organelles and inclusion bodies. Non-detergent sulfobetaines (NDSB), although not detergents, possess hydrophilic groups similar to those of zwitterionic detergents but with shorter hydrophobic chains. Sulfobetaines do not form micelles. They have been reported to improve the yield of membrane proteins when used with detergents and prevent aggregation of denatured proteins.

DEFINITION www.citycollegiate.com Detergents are soap-like compounds which are used for cleaning purpose. They are sodium salts of long chain alkyl benzene sulphonic acids or sodium salts of long chain alkyl hydrogen sulphate, whereas, soaps are sodium salts of long chain carboxylic acids. The general formulae of soaps and detergents are:

Detergents may be used in hard water without the formation of scum. This is the advantage of a detergent over soap which gives curdles when used with hard water. STRUCTURE OF www.citycollegiate.com DETERGENTS A detergent consists of two parts: Hydrophilic part (water soluble) Hydrophobic part (oil soluble) Hydrophilic part Hydrophilic part is sodium salt which is readily soluble in water. e.g. SO3-, OSO3-, OH- or NR4. This part of a detergent is ionic and is attracted by polar water molecules. Hydrophobic part hydrocarbon part of detergent is called hydrophobic part. It is non-polar . Hydrophobic part is insoluble in water but it is soluble in oil. This part consists of a hydrocarbon segment and can dissolve oil or grease. For latest information , free computer courses and high impact notes visit : www.citycollegiate.com CLEANING ACTION When a greasy cloth is put into aqueous solution of a detergent, The hydrophilic part of detergent is dissolved in water while hydrophobic part dissolves grease or oil like substances on the cloth. On slight agitation grease is readily removed from the cloth. ADVANTAGE OF www.citycollegiate.com DETERGENT See difference between soap and detergent. DISADVANTAGE OF DETERGENT Hydrocarbon chain of detergent does not broken by bacteria and bacteria remain in the solution. DIFFERENCE BETWEEN SOAP AND DETERGENT SOAP DETERGENT Soaps are sodium salts of long chain carboxylic acids. It is obtained by natural resources i.e. fats and oils. Calcium and magnesium salts of soaps are insoluble in water. Detergents are sodium salts of long chain alkyl benzene sulphonic acids or alkyl sulphate. Detergents are synthetic materials. Calcium and magnesium salts of detergents are soluble in water.

In hard water it produces scum Hard water does not affect its cleaning which affect its cleaning action. action. For latest information , free computer courses and high impact notes visit : www.citycollegiate.com


Nonionic detergents, which form electrically neutral colloidal particles in solution, contain non -ionic emulsifiers, amplifying the ability to remove oily residues. These nonionic surfactants are low-foaming and have defoaming properties that improve wetting, rinsing and particle removal while not hindering with mechanical labor. A common nonionic detergent is Liquinox used to clean glassware and does not react with hard water ions; this is due to the fact that no ionic groups exist to do so. In addition, it foams less than ionic detergents but has some polar portions to provide necessary water solubility. Cationic detergents often come in powder foam and have a long cationic chain that is responsible for surfactant properties. However, cationic detergents are poor detergents even though they have adequate emulsifying properties. Instead, there are often used in bacterica/germ free environments due to their antiseptic properties. Anionic detergents are based on sulfate or carboxylate anions and are of the most common modern synthetic detergents producing negative charged colloidal ions in solution. Bile salts in the stomach have emulsifying properties in the digestive system, reacting with fats and oils as a detergent to form smaller particles of the consumed compounds. In addition, the same amphipathic properties that allow bile acids to emulsify using lipids also make them membrane-disruptive mediums.

The structure of detergent

For soapy detergent: the ionic head should be

For soapless detergent: the ionic head may be

Technical Centre Technical Support

Detergents are chemicals designed to assist in the removal of soil from a surface and are available as powders, liquids, foams or gels. Detergents have two modes of action (physical & chemical) depending on their makeup and the soil they are acting upon. When selecting a detergent, the following points should be considered: Type of soil to be removed Cleaning method required Cleaning equipment available Will disinfection be required Time window Water hardness Chemical concentration required Water temperature Materials of construction Operator safety Risk to food safety Cost

Detergent Components Surfactants (Surface Active Agents) are an important part of any detergent as they enable the detergent to increase the wetting power of water by reducing its surface tension. This ability increases the contact between the soil and the detergent solution and allows it to penetrate the minute irregularities of the dirt more effectively. Four types of surfactants are available, which are: Anionic - the active part is negatively charged and generally is a good foamer and has good wetting properties. Cationic - the active part is positively charged and generally is biocidal. Amphoteric - which is cationic in acid medium and anionic in alkaline medium. Can sometimes be biocidal. Non-ionic surfactant, these have no overall charge but are very good emulsifying agents. Sequestrants counteract the effect of water hardness salts, preventing the formation of scale drop out. Scale drop out on surfaces provides a barrier to cleaning and a place where microbes can reside and grow. Sequestrants bind the calcium/magnesium ions in the hard water to form soluble complexes and thereby prevent scale formation. The level of sequestrant in the detergent and the detergent concentration must be matched to the water hardness and mineral salts that may be present in the soil to be removed. The base of a detergent will determine what type of detergent it is alkaline, acid or neutral. For example in an alkaline detergent, the base is usually caustic soda (sodium hydroxide). In some cases, the detergent may have a chlorine donor that is added to assist in protein and stain removal. The chlorine donor is there primarily for this purpose and not as a biocide. Inhibitors are sometimes added to detergents to reduce the attack on the metal surface (for instance inhibitors added to hydrochloric acid formulations - Descaler). Alternatively, the formulation may be designed to prevent attack on soft metals such as aluminium, tin and brass (Silicated alkaline products - Chlorfoam 2000). Alkaline and Caustic detergents are probably the most common detergents used throughout the food industry as they have good fat and protein removal properties and they can be used across a wide spectrum of food manufacturing environments. Both contain sodium hydroxide boosted with surfactants and sequestrants. Caustic detergents contain higher levels of Sodium Hydroxide and generally have higher risk classifications than alkaline detergents. They are corrosive to skin and should always be used in conjunction with the correct Personal Protective Equipment. They may also attack soft metals such as aluminium, tin, brass etc. Acid Detergents These are used mainly for protein, mineral and vegetable deposit removal and typically contain phosphoric acid. Acids must never be allowed to come into contact with chlorine compounds because of the consequential release of chlorine gas, which can prove to be fatal. Neutral Detergents These are generally blends of surfactants used for manual dishwashing and manual cleaning. They are generally safe to use and are found predominantly in domestic and light industrial use. Gloves should still be worn to avoid de-fatting of the skin and to reduce the risk of dermatitis. Types of Soil There are essentially two types of soil: Organic These are derived from living matter and include animal fat, vegetable oils, starch, sugars, and proteins from milk, egg, meat or blood. Normally they can be removed by using neutral or alkaline detergents, but if heated, dried or allowed to remain for a prolonged period then caustic detergents may be required to remove them.

When removing liquid protein deposits such as egg, blood or meat it is best practice to begin with a cold water rinse first to prevent cooking of the protein. When grease or oil is heated it will form a resolute, dark, sticky polymerised deposit, which can generally be removed with an alkaline detergent. If the polymerised deposit is heated further it results in the formation of carbon, which generally has to be removed by a more aggressive caustic alkali detergent such as sodium hydroxide. Inorganic These include water hardness salts (scale), oxidised metals (rust), uric acid salts (urinal stains), beerstone and calcium salts deposited from milk (milkstone). These types of soils are usually removed with acids such as hydrochloric and phosphoric. Soils are very rarely made up of one component, for example a hard scale in a meat processing area may be a complex of a mineral scale and protein. Water Chemistry All water used for domestic and industrial purposes will have hard water salts (calcium and magnesium ions) present. Water hardness is a measurement of the level of these dissolved solids in the water. These solids may come out of solution and precipitate as a scale under certain conditions; namely: An increase in water temperature highest effect as water is raised to boiling point. As the pH of water is increased; e.g. by adding an alkaline detergent. The level of hard water salts varies from area to area in the UK, for example, water used in some areas of the north of Scotland will have less than 60ppm (parts per million as CaCO3) hard water salts because the water is generally surface water held in reservoirs and has not passed through limestone deposits. In areas such as the South East where the underlying rock is limestone, water hardness can easily be over 600ppm.

1. Alkaline Detergents
It is the main detergent ingredient, able to combine with fats and oils to form soap and dissolves proteins which can be remove by water. However it is corrosive due to its high level of active alkalinity and it is harmful to the human body as alkaline dissolves the phospholipid layers on our body. Hence, Alkalinity, corrosiveness, effectiveness in cleaning. Alkaline detergents are also commonly use in food processing and food service industries. General household detergents are home-grade detergents with mild level of alkaline that is able to remove fresh soil from floors, walls, ceilings, preparation surfaces, most equipment and utensils. Highly alkaline cleaners (Heavy-duty detergents) that remove wax, aged or dried soil, and baked-on grease.

Examples of alkaline detergents

Sodium Hydroxide (NaOH): Known as caustic soda/ lye Strongest and cheapest alkaline Capable of dissolving protein and turn fat to soap Precipitate calcium and magnesium in water Usually use to remove heavy soils Not suitable for certain meta equipments. (E.g. Aluminium as NaOH will cause these metals to be integrated into the food) Hard to remove by rinsing Highly corrosive on all surfaces (including skin) Wetting agents (Emulsifiers) can be added to improve rinsing properties while preventing its corrosive abilities

Sodium Metasilicate: Less corrosive and effectiveness than NaOH Safer to handle To prevent soil detergent mixture from precipitating should be used at water temp. >62oC Good rinsing and wetting properties Sodium Carbonate: Mild alkalis Act as a buffering agent Less effective than NaOH and sodium Metasilicate Non-corrosive Safe to handle Rarely use in industries Used for cleaning hands

2. Acid Detergents

It involves acid as the major component which is used in dissolving mineral deposits (Calcium and Magnesium precipitates) or hard water deposits from equipment surfaces. Removing mineral deposits effectively with acid detergents as compared to alkaline detergents or other cleaners. Two main groups of acid detergents: Inorganic (HCL, H2SO4) , Organic (Vinegar, Citric Acid).

Examples of acid detergents

1. Inorganic Acids: Known as mineral acids/ strong acids Examples: Hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid (Highly corrosive) Excellent for removing and controlling mineral deposits, rust, alkaline Irritation to skin and extremely corrosive 2. Organic Acids: Milder acid than inorganic Examples: Citric, Tartaric( Found in Grapes) Less corrosive to metals Less irritation to skin as compare to inorganic acids

3. Degreasers
Consists surfactants (complex molecule, reduces the surface tension of water when added to water to allow closer contact between the soil deposit and the cleaning medium). It is use for removing grease and greasy soil and able to penetrate and hydrolyze fats and oils into smaller particles to be then removed by water.

4. Abrasive Detergents
It is a powder or paste than contains abrasives like pumice, quartz or sand. Abrasive is usually ground into small particles size and is use on equipment surfaces that requires scrubbing, scouring or polishing. However, it can cause scratches on metal surfaces and it needs to be washed away completely to prevent contamination of food.

5. Detergent Sanitizers
Detergent Sanitizers contain a sanitizer/ disinfectants with a detergent and it cleans and sanitize in one operation which saves time and labour as well. It also function as a detergent for heavy soil and sensitive areas. There are 3 major types of detergent sanitizers: Alkaline detergents + Hypochlorite (Assist in removing protein residues) - Alkaline Detergents (Not containing an anionic surfactant) + Quaternary Ammonium Coumpound - - Acid Detergent + iodophor (iodine- containing material)

How to choose detergents?





Type of soil to be removed - Type of material to be clean so that the detergent does not damage it Type of cleaning technique - Manual Labour, do not use excessive acid or alkaline detergents

Detergent is a material that helps in cleaning. Detergent contains one of more surfactants which are capable of reducing the surface tension of liquid such as water. Commonly, detergent consists of long chain hydrocarbon and ionic group (such as alky sulfate or derivative of ammoniac group). [edit]Types Anionic These detergents are man-made and consist of long hydrocarbon chains and a water-soluble ionic group, which is usually negatively charged. These detergents are commonly known as surfactants, or alkyl benzene sulfonates Cationic

of Detergents

These detergents are also man-made, and they only differ from anionic detergents in that the watersoluble ionic group is positively charged. These detergents are primarily derivatives of ammonium and are commonly used as a germicide and in shampoo. Neutral These type of detergents contain the same general set up as all other detergents, except its overall charge is neutral. The head of the detergent is polar due to the presence of three hydroxyl groups and an ester group. Natural Natural detergents such as bile salts (sodiumglycoholate) are made in the liver. These detergents are derivatives of cholesterol, a type of lipid. Its main function is digestion. The bile salt is capable of emulsifying fats and oils such that enzymes may break them down further. [edit]Function

and Application