In chemistry, a soap is a salt of a fatty acid.IUPAC. " IUPAC Gold Book – soap" Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. . . Accessed 2010-08-09 Household uses for soaps include washing, bathing, and other types of housekeeping, where soaps act as , emulsifying oils to enable them to be carried away by water. In industry they are also used in textile spinning and are important components of some . Metal soaps are also included in modern artists' oil paints formulations as a rheology modifier.
Soaps for cleaning are obtained by treating vegetable or animal oils and fats with a strong base, such as sodium hydroxide or potassium hydroxide in an aqueous solution. Fats and oils are composed of ; three molecules of fatty acids attach to a single molecule of glycerol.Cavitch, Susan Miller. The Natural Soap Book. Storey Publishing, 1994 . The alkaline solution, which is often called lye (although the term "lye soap" refers almost exclusively to soaps made with sodium hydroxide), induces saponification.
In this reaction, the triglyceride fats first Hydrolysis into free fatty acids, and then the latter combine with the alkali to form crude soap: an amalgam of various soap salts, excess fat or alkali, water, and liberated glycerol (glycerin). The glycerin, a useful byproduct, can remain in the soap product as a softening agent, or be isolated for other uses.
Soaps are key components of most lubricating greases, which are usually emulsions of calcium stearate or lithium stearate and mineral oil.see the main Grease (lubricant) article Many other metallic soaps are also useful, including those of aluminium, sodium, and mixtures of them. Such soaps are also used as thickeners to increase the viscosity of oils. In ancient times, lubricating greases were made by the addition of lime to olive oil.Thorsten Bartels et al. "Lubricants and Lubrication" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Weinheim.
|+ Fatty acid content of various fats used for soapmaking|
|+ ! !! Lauric acid!! Myristic acid!! Palmitic acid!! Stearic acid!! Oleic acid!! Linoleic acid!! Linolenic acid|
The Ebers papyrus (Egypt, 1550 BC) indicates the bathed regularly and combined animal and vegetable oils with alkaline salts to create a soap-like substance. Egyptian documents mention a soap-like substance was used in the preparation of wool for weaving.
A popular belief claims soap takes its name from a supposed Mount Sapo, where animal sacrifices were supposed to have taken place; tallow from these sacrifices would then have mixed with ashes from fires associated with these sacrifices and with water to produce soap, but there is no evidence of a Mount Sapo in the Roman world and no evidence for the story. The Latin word sapo simply means "soap"; it was likely borrowed from an early Germanic language and is cognate with Latin sebum, "tallow", which appears in Pliny the Elder's account. soap. Etymonline.com. Retrieved on 2011-11-20. Roman animal usually burned only the bones and inedible entrails of the sacrificed animals; edible meat and fat from the sacrifices were taken by the humans rather than the gods.
Zosimos of Panopolis, circa 300 AD, describes soap and soapmaking. Galen describes soap-making using lye and prescribes washing to carry away impurities from the body and clothes. The use of soap for personal cleanliness became increasingly common in the 2nd century A.D. According to Galen, the best soaps were Germanic, and soaps from Gaul were second best. This is a reference to true soap in antiquity.
A 12th-century Islamic document describes the process of soap production.BBC Science and Islam Part 2, Jim Al-Khalili. BBC Productions. Accessed 30 January 2012. It mentions the key ingredient, alkali, which later becomes crucial to modern chemistry, derived from al-qaly or "ashes".
In France, by the second half of the 15th century, the semi-industrialized professional manufacture of soap was concentrated in a few centers of Provence—Toulon, Hyères, and Marseille—which supplied the rest of France. In Marseilles, by 1525, production was concentrated in at least two factories, and soap production at Marseille tended to eclipse the other Provençal centers.Barthélemy, L. (1883) "La savonnerie marseillaise", noted by Nef 1936:660 note 99. English manufacture tended to concentrate in London.Nef 1936:653, 660.
Finer soaps were later produced in Europe from the 16th century, using vegetable oils (such as olive oil) as opposed to animal fats. Many of these soaps are still produced, both industrially and by small-scale artisans. Castile soap is a popular example of the vegetable-only soaps derived from the oldest "white soap" of Italy.
In modern times, the use of soap has become commonplace in industrialized nations due to a better understanding of the role of hygiene in reducing the population size of pathogenic microorganisms. Industrially manufactured bar soaps became available in the late 18th century, as advertising campaigns in Europe and America promoted popular awareness of the relationship between cleanliness and health.
Until the Industrial Revolution, soapmaking was conducted on a small scale and the product was rough. In 1780 James Keir established a chemical works at Tipton, for the manufacture of alkali from the sulfates of potash and soda, to which he afterwards added a soap manufactory. The method of extraction proceeded on a discovery of Keir's. Andrew Pears started making a high-quality, transparent soap in 1807 in London. His son-in-law, Thomas J. Barratt, opened a factory in Isleworth in 1862.
During the Restoration era (February 1665 – August 1714) a soap tax was introduced in England, which meant that until the mid-1800's, soap was a luxury, used regularly only by the well-to-do. The soap manufacturing process was closely supervised by revenue officials who made sure that soapmakers' equipment was kept under lock and key when not being supervised. Moreover, soap could not be produced by small makers because of a law which stipulated that soap boilers must manufacture a minimum quantity of one imperial ton at each boiling, which placed the process beyond reach of the average person. The soap trade was boosted and deregulated when the tax was repealed in 1853.
William Gossage produced low-priced, good-quality soap from the 1850s. Robert Spear Hudson began manufacturing a soap powder in 1837, initially by grinding the soap with a mortar and pestle. American manufacturer Benjamin T. Babbitt introduced marketing innovations that included sale of bar soap and distribution of . William Hesketh Lever and his brother, James, bought a small soap works in Warrington in 1886 and founded what is still one of the largest soap businesses, formerly called Lever Brothers and now called Unilever. These soap businesses were among the first to employ large-scale advertising campaigns.
In the early 1900s, other companies began to develop their own liquid soaps. Such products as Pine-Sol and Tide appeared on the market, making the process of cleaning things other than skin, such as clothing, floors, and bathrooms, much easier.
Handmade soap from the cold process also differs from industrially made soap in that an excess of fat is used, beyond that needed to consume the alkali (in a cold-pour process, this excess fat is called "superfatting"), and the glycerol left in acts as a moisturizing agent. However, the glycerine also makes the soap softer and less resistant to becoming "mushy" if left wet. Since it is better to add too much oil and have left-over fat, than to add too much lye and have left-over lye, soap produced from the hot process also contains left-over glycerol and its concomitant pros and cons. Further addition of glycerol and processing of this soap produces glycerin soap. Superfatted soap is more skin-friendly than one without extra fat. However, if too much fat is added, it can leave a "greasy" feel to the skin. Sometimes, an Moisturizer additive, such as jojoba oil or shea butter, is added "at trace" (i.e., the point at which the saponification process is sufficiently advanced that the soap has begun to thicken in the cold process method) in the belief that nearly all the lye will be spent and it will escape saponification and remain intact. In the case of hot-process soap, an emollient may be added after the initial oils have saponified so they remain unreacted in the finished soap. Superfatting can also be accomplished through a process known as "lye discount" in which the soap maker uses less alkali than required instead of adding extra fats.
Even in the cold soap making process, some heat is usually required; the temperature is usually raised to a point sufficient to ensure complete melting of the fat being used. The batch may also be kept warm for some time after mixing to ensure the Lye is completely used up. This soap is safe to use after about 12–48 hours, but is not at its peak quality for use for several weeks.
Cold-process soapmaking requires exact measurements of lye and fat amounts and computing their ratio, using saponification charts to ensure the finished product does not contain any excess hydroxide or too much free unreacted fat. Saponification charts should also be used in hot processes, but are not necessary for the "fully boiled hot-process" soaping.
Historically, lye used in the cold process was made from scratch using rainwater and ashes. Soapmakers considered the lye solution ready for use when an egg would float in it. Homemade lye making for this process was unpredictable and therefore eventually led to the isolation of sodium hydroxide by English chemist Sir Humphry Davy in the early 1800s.
A cold-process soapmaker first looks up the saponification value for each unique fat on an oil specification sheet. Oil specification sheets contain laboratory test results for each fat, including the precise saponification value of the fat. The saponification value for a specific fat varies by season and by specimen species. This value is used to calculate the exact amount of sodium hydroxide to react with the fat to form soap. The saponification value must be converted into an equivalent sodium hydroxide value for use in cold process soapmaking. Excess unreacted lye in the soap results in a very high pH and can burn or irritate skin, whereas not enough lye leaves the soap greasy. Most soap makers formulate their recipes with a 2–5% deficit of lye, to account for the unknown deviation of saponification value between their oil batch and laboratory averages.
The lye is dissolved in water. Then, the oils are heated, or melted if they are solid at room temperature. Once the oils are liquefied and the lye is fully dissolved in water, they are combined. This lye-fat mixture is mixed until the two phases (oils and water) are fully emulsified. Emulsion is most easily identified visually when the soap exhibits some level of "trace," which is the thickening of the mixture. Many modern-day amateur soapmakers use a stick blender to speed up this process. Varying levels of trace can occur at each stage of the saponification process. Depending on how additives affect trace, they may be added at light trace, medium trace, or heavy trace. After much stirring, the mixture turns to the consistency of a thin pudding. "Trace" corresponds roughly to viscosity. and can be added with the initial soaping oils, but solid additives such as botanicals, herbs, oatmeal, or other additives are most commonly added at light trace, just as the mixture starts to thicken.
The batch is then poured into molds, kept warm with towels or blankets, and left to continue saponification for 12 to 48 hours. (Milk soaps or other soaps with sugars added are the exception. They typically do not require insulation, as the presence of sugar increases the speed of the reaction and thus the production of heat.) During this time, it is normal for the soap to go through a "gel phase," wherein the opaque soap will turn somewhat transparent for several hours, before once again turning opaque.
After the insulation period, the soap is firm enough to be removed from the mold and cut into bars. At this time, it is safe to use the soap, since saponification is in essence complete. However, cold-process soaps are typically cured and hardened on a drying rack for 2–6 weeks before use. During this cure period, trace amounts of residual lye are consumed by saponification and excess water evaporates.
During the curing process, some molecules in the outer layer of the solid soap react with the carbon dioxide of the air and produce a dusty sheet of sodium carbonate. This reaction is more intense if the mass is exposed to wind or low temperatures.
In the hot process, the hydroxide and the fat are heated and mixed together at 80–100 °C, a little below boiling point, until saponification is complete, which, before modern scientific equipment, the soapmaker determined by taste (the sharp, distinctive taste of the hydroxide disappears after it is saponified) or by eye; the experienced eye can tell when gel stage and full saponification has occurred. Beginners can find this information through research and classes. Tasting soap for readiness is not recommended, as sodium and potassium hydroxides, when not saponified, are highly caustic.
An advantage of the fully boiled hot process in soapmaking is the exact amount of hydroxide required need not be known with great accuracy. They originated when the purity of the alkali hydroxides were unreliable, as these processes can use even naturally found alkalis, such as wood ashes and potash deposits. In the fully boiled process, the mix is actually boiled (100+ °C), and, after saponification has occurred, the "neat soap" is precipitated from the solution by adding common salt, and the excess liquid is drained off. This excess liquid carries away with it much of the impurities and color compounds in the fat, to leave a purer, whiter soap, and with practically all the glycerine removed. The hot, soft soap is then pumped into a mold. The spent hydroxide solution is processed for recovery of glycerine.
At this stage, the soap still contains too much water, which has to be removed. This was traditionally done on chill rolls, which produced the soap flakes commonly used in the 1940s and 1950s. This process was superseded by spray dryers and then by vacuum dryers.
The dry soap (about 6–12% moisture) is then compacted into small pellets or noodles. These pellets or noodles are then ready for soap finishing, the process of converting raw soap pellets into a saleable product, usually bars.
Soap pellets are combined with fragrances and other materials and blended to homogeneity in an amalgamator (mixer). The mass is then discharged from the mixer into a refiner, which, by means of an auger, forces the soap through a fine wire screen. From the refiner, the soap passes over a roller mill (French milling or hard milling) in a manner similar to calendering paper or plastic or to making chocolate liquor. The soap is then passed through one or more additional refiners to further plasticize the soap mass. Immediately before extrusion, the mass is passed through a vacuum chamber to remove any trapped air. It is then extruded into a long log or blank, cut to convenient lengths, passed through a metal detector, and then stamped into shape in refrigerated tools. The pressed bars are packaged in many ways.
Sand or pumice may be added to produce a soap. The scouring agents serve to remove dead cells from the skin surface being cleaned. This process is called exfoliation. Many newer materials that are effective, yet do not have the sharp edges and poor particle size distribution of pumice, are used for exfoliating soaps.
To make antibacterial soap, compounds such as triclosan or triclocarban can be added. There is some concern that use of antibacterial soaps and other products might encourage antibiotic resistance in microorganisms.