Saponification

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Saponification is a process of cleaving esters into carboxylate salts and alcohols by the action of aqueous alkali. Typically aqueous sodium hydroxide solutions are used. [1] [2] It is an important type of alkaline hydrolysis. When the carboxylate is long chain, its salt is called a soap. The saponification of ethyl acetate gives sodium acetate and ethanol:

Contents

C2H5O2CCH3 + NaOH → C2H5OH + NaO2CCH3

Saponification of fats

Vegetable oils and animal fats are the traditional materials that are saponified. These greasy materials, triesters called triglycerides, are usually mixtures derived from diverse fatty acids. In the traditional saponification, the triglyceride is treated with lye, which cleaves the ester bonds, releasing fatty acid salts (soaps) and glycerol. In one simplified version, the saponification of stearin gives sodium stearate.

C3H5(O2C(CH2)16CH3)3 + 3 NaOH → C3H5(OH)3 + 3 NaO2C(CH2)16CH3

This process is the main industrial method for producing glycerol (C3H5(OH)3).

Some soap-makers leave the glycerol in the soap. Others precipitate the soap by salting it out with sodium chloride.

Skeletal formula of stearin, a triglyceride that is converted by saponification with sodium hydroxide into glycerol and sodium stearate. Stearin.png
Skeletal formula of stearin, a triglyceride that is converted by saponification with sodium hydroxide into glycerol and sodium stearate.

Fat in a corpse converts into adipocere, often called "grave wax". This process is more common where the amount of fatty tissue is high and the agents of decomposition are absent or only minutely present.

Saponification value

The saponification value is the amount of base required to saponify a fat sample. [3] Soap makers formulate their recipes with a small deficit of lye to account for the unknown deviation of saponification value between their oil batch and laboratory averages.

Mechanism of basic hydrolysis

The hydroxide anion adds to the carbonyl group of the ester. The immediate product is called an orthoester.

Saponification part I Verseifungsreaktion 1.svg
Saponification part I

Expulsion of the alkoxide generates a carboxylic acid:

Saponification part II Verseifungsreaktion 2.svg
Saponification part II

The alkoxide ion is a strong base so the proton is transferred from the carboxylic acid to the alkoxide ion, creating an alcohol:

saponification part III Verseifungsreaktion 3.svg
saponification part III

In a classic laboratory procedure, the triglyceride trimyristin is obtained by extracting it from nutmeg with diethyl ether. Saponification to the soap sodium myristate takes place using NaOH in water. Treating the soap with hydrochloric acid gives myristic acid. [4]

Saponification of fatty acids

The reaction of fatty acids with base is the other main method of saponification. In this case, the reaction involves neutralization of the carboxylic acid. The neutralization method is used to produce industrial soaps such as those derived from magnesium, the transition metals, and aluminium. This method is ideal for producing soaps that are derived from a single fatty acid, which leads to soaps with predictable physical properties, as required by many engineering applications.

Applications

Hard and soft soaps

Depending on the nature of the alkali used in their production, soaps have distinct properties. Sodium hydroxide (NaOH) produces "hard" soaps; hard soaps can also be used in water containing Mg, Cl, and Ca salts. [5] By contrast, potassium soaps (derived using KOH) are "soft" soaps. The fatty acid source also affects the soap's melting point. Most early hard soaps were manufactured using animal fats and KOH extracted from wood ash; these were broadly solid. However, the majority of modern soaps are manufactured from polyunsaturated triglycerides such as vegetable oils. As in the triglycerides they are formed from [6] the salts of these acids have weaker inter-molecular forces and thus lower melting points.

Lithium soaps

Lithium 12-hydroxystearate and other lithium-based fatty acids are important constituents of lubricating greases. In lithium-based greases, lithium carboxylates are thickeners. "Complex soaps" are also common, these being combinations of more than one acid salt, such as azelaic or acetic acid. [7]

Fire extinguishers

Fires involving cooking fats and oils (classified as class K (US) or F (Australia/Europe/Asia)) burn hotter than most flammable liquids, rendering a standard class B extinguisher ineffective. Such fires should be extinguished with a wet chemical extinguisher. Extinguishers of this type are designed to extinguish cooking fats and oils through saponification. The extinguishing agent rapidly converts the burning substance to a non-combustible soap.

Oil paints

Detail of Madame X (Madame Pierre Gautreau), John Singer Sargent, 1884, showing saponification in the black dress. Detail of Madame X (Madame Pierre Gautreau), John Singer Sargent, 1884.jpg
Detail of Madame X (Madame Pierre Gautreau), John Singer Sargent, 1884, showing saponification in the black dress.

Saponification can occur in oil paintings over time, causing visible damage and deformation. Oil paints are composed of pigment molecules suspended in an oil-binding medium. Heavy metal salts are often used as pigment molecules, such as in lead white, red lead, and zinc white. [8] If those heavy metal salts react with free fatty acids in the oil medium, metal soaps may form in a paint layer that can then migrate outward to the painting's surface. [9] :12–19

Saponification in oil paintings was described as early as 1912. [10] :151 It is believed to be widespread, having been observed in many works dating from the fifteenth through the twentieth centuries; works of different geographic origin; and works painted on various supports, such as canvas, paper, wood, and copper. Chemical analysis may reveal saponification occurring in a painting's deeper layers before any signs are visible on the surface, even in paintings centuries old. [9] :16

The saponified regions may deform the painting's surface through the formation of visible lumps or protrusions that can scatter light. These soap lumps may be prominent only on certain regions of the painting rather than throughout. In John Singer Sargent's famous Portrait of Madame X , for example, the lumps only appear on the blackest areas, which may be because of the artist's use of more medium in those areas to compensate for the tendency of black pigments to soak it up. [9] :12–13,15 The process can also form chalky white deposits on a painting's surface, a deformation often described as "blooming" or "efflorescence", and may also contribute to the increased transparency of certain paint layers within an oil painting over time. [9] :16,19

Saponification does not occur in all oil paintings and many details are unresolved. [9] :19 At present, retouching is the only known restoration method.

See also

Related Research Articles

<span class="mw-page-title-main">Carboxylic acid</span> Organic compound containing a –C(=O)OH group

In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group attached to an R-group. The general formula of a carboxylic acid is often written as R−COOH or R−CO2H, sometimes as R−C(O)OH with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic acids occur widely. Important examples include the amino acids and fatty acids. Deprotonation of a carboxylic acid gives a carboxylate anion.

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

Hydrolysis is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution, elimination, and solvation reactions in which water is the nucleophile.

<span class="mw-page-title-main">Triglyceride</span> Any ester of glycerol having all three hydroxyl groups esterified with fatty acids

A triglyceride is an ester derived from glycerol and three fatty acids. Triglycerides are the main constituents of body fat in humans and other vertebrates, as well as vegetable fat. They are also present in the blood to enable the bidirectional transference of adipose fat and blood glucose from the liver, and are a major component of human skin oils.

<span class="mw-page-title-main">Soap</span> Substance used for cleaning

Soap is a salt of a fatty acid used in a variety of cleansing and lubricating products. In a domestic setting, soaps are surfactants usually used for washing, bathing, and other types of housekeeping. In industrial settings, soaps are used as thickeners, components of some lubricants, and precursors to catalysts.

<span class="mw-page-title-main">Stearin</span> Chemical compound

Stearin, or tristearin, or glyceryl tristearate is an odourless, white powder. It is a triglyceride derived from three units of stearic acid. Most triglycerides are derived from at least two and more commonly three different fatty acids. Like other triglycerides, stearin can crystallise in three polymorphs. For stearin, these melt at 54 (α-form), 65, and 72.5 °C (β-form).

<span class="mw-page-title-main">Glyceride</span> Chemical esters commonly found in fats and oils

Glycerides, also known as acylglycerols, are esters formed from glycerol and fatty acids, and are generally very hydrophobic.

<span class="mw-page-title-main">Stearic acid</span> Eighteen-carbon straight-chain fatty acid

Stearic acid is a saturated fatty acid with an 18-carbon chain. The IUPAC name is octadecanoic acid. It is a soft waxy solid with the formula CH3(CH2)16CO2H. The triglyceride derived from three molecules of stearic acid is called stearin. Stearic acid is a prevalent fatty-acid in nature, found in many animal and vegetable fats, but is usually higher in animal fat than vegetable fat. It has a melting point of 69.4 °C and a pKa of 4.50.

<span class="mw-page-title-main">Palmitic acid</span> Chemical compound

Palmitic acid is a fatty acid with a 16-carbon chain. It is the most common saturated fatty acid found in animals, plants and microorganisms. Its chemical formula is CH3(CH2)14COOH, and its C:D is 16:0. It is a major component of the oil from the fruit of oil palms, making up to 44% of total fats. Meats, cheeses, butter, and other dairy products also contain palmitic acid, amounting to 50–60% of total fats. Palmitates are the salts and esters of palmitic acid. The palmitate anion is the observed form of palmitic acid at physiologic pH (7.4). Major sources of C16:0 are palm oil, palm kernel oil, coconut oil, and milk fat.

<span class="mw-page-title-main">Drying oil</span> Oil that hardens after exposure to air

A drying oil is an oil that hardens to a tough, solid film after a period of exposure to air, at room temperature. The oil hardens through a chemical reaction in which the components crosslink by the action of oxygen. Drying oils are a key component of oil paint and some varnishes. Some commonly used drying oils include linseed oil, tung oil, poppy seed oil, perilla oil, and walnut oil. Their use has declined over the past several decades, as they have been replaced by alkyd resins and other binders.

Biodiesel production is the process of producing the biofuel, biodiesel, through the chemical reactions of transesterification and esterification. This involves vegetable or animal fats and oils being reacted with short-chain alcohols. The alcohols used should be of low molecular weight. Ethanol is the most used because of its low cost, however, greater conversions into biodiesel can be reached using methanol. Although the transesterification reaction can be catalyzed by either acids or bases, the base-catalyzed reaction is more common. This path has lower reaction times and catalyst cost than those acid catalysis. However, alkaline catalysis has the disadvantage of high sensitivity to both water and free fatty acids present in the oils. August 10 is international biodiesel day

<span class="mw-page-title-main">Saponification value</span> Milligrams of a base required to saponify 1g of fat

Saponification value or saponification number represents the number of milligrams of potassium hydroxide (KOH) or sodium hydroxide (NaOH) required to saponify one gram of fat under the conditions specified. It is a measure of the average molecular weight of all the fatty acids present in the sample in form of triglycerides. The higher the saponification value, the lower the fatty acids average length, the lighter the mean molecular weight of triglycerides and vice versa. Practically, fats or oils with high saponification value are more suitable for soap making.

In chemistry, acid value is a number used to quantify the acidity of a given chemical substance. It is the quantity of base, expressed as milligrams of KOH required to neutralize the acidic constituents in 1 gram of a sample. The acid value measures the acidity of water-insoluble substances like oils, fats, waxes and resins, which do not have a pH value.

<span class="mw-page-title-main">Carboxylate</span> Chemical group (RCOO); conjugate base of a carboxylic acid

In organic chemistry, a carboxylate is the conjugate base of a carboxylic acid, RCOO. It is an ion with negative charge.

<span class="mw-page-title-main">Sodium stearate</span> Chemical compound

Sodium stearate is the sodium salt of stearic acid. This white solid is the most common soap. It is found in many types of solid deodorants, rubbers, latex paints, and inks. It is also a component of some food additives and food flavorings.

Oleochemistry is the study of vegetable oils and animal oils and fats, and oleochemicals derived from these fats and oils. The resulting product can be called oleochemicals (from Latin: oleum "olive oil"). The major product of this industry is soap, approximately 8.9×106 tons of which were produced in 1990. Other major oleochemicals include fatty acids, fatty acid methyl esters, fatty alcohols and fatty amines. Glycerol is a side product of all of these processes. Intermediate chemical substances produced from these basic oleochemical substances include alcohol ethoxylates, alcohol sulfates, alcohol ether sulfates, quaternary ammonium salts, monoacylglycerols (MAG), diacylglycerols (DAG), structured triacylglycerols (TAG), sugar esters, and other oleochemical products.

In the food industry and biochemistry, interesterification (IE) is a process that rearranges the fatty acids of a fat product, typically a mixture of triglycerides. The process implies breaking and reforming the ester bonds C–O–C that connect the fatty acid chains to the glycerol hubs of the fat molecules. The reactions involve catalysts, either inorganic chemicals or enzymes.

<span class="mw-page-title-main">Hard soap</span>

Hard soaps, also termed soda soaps in older terminology, are categorized under soaps and are typically sodium salts of fatty acids. They vary in color from white to brownish and have a fatty acid content ranging from 72 to 75%. These soaps are typically made from lower-quality fats. Hard soaps serve as the foundation for products frequently labeled as fine soaps, which are fortified with nourishing additives, perfumes, and dyes.

Saltwater soap, also called sailors' soap, is a potassium-based soap for use with seawater. Inexpensive common commercial soap will not lather or dissolve in seawater due to high levels of sodium chloride in the water. Similarly, common soap does not work as well as potassium-based soap in hard water where calcium replaces the sodium, making residual insoluble "scum" due to the insolubility of the soap residue. To be an effective cleaning agent, soap must be able to dissolve in water.

<span class="mw-page-title-main">Alkoxide</span> Conjugate base of an alcohol

In chemistry, an alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as RO, where R is the organyl substituent. Alkoxides are strong bases and, when R is not bulky, good nucleophiles and good ligands. Alkoxides, although generally not stable in protic solvents such as water, occur widely as intermediates in various reactions, including the Williamson ether synthesis. Transition metal alkoxides are widely used for coatings and as catalysts.

References

  1. "Saponification | chemical reaction". Encyclopedia Britannica. Retrieved 2021-05-23.
  2. Smith, Michael B.; March, Jerry (2007), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (6th ed.), New York: Wiley-Interscience, ISBN   978-0-471-72091-1
  3. "Quality Laboratory Oil Examination Procedures and Practices". American Oil Chemists' Society. Archived from the original on 25 December 2012. Retrieved 17 December 2012.
  4. G. D. Beal (1926). "Myristic Acid". Organic Syntheses. 6: 66. doi:10.15227/orgsyn.006.0066.
  5. "How Saponification Makes Soap". ThoughtCo. Retrieved 2023-07-05.
  6. "Double bonds and hydrogenation". GCSE Bitesize. BBC. Archived from the original on 2018-08-18. Retrieved 2017-03-10.
  7. Bartels, Thorsten; Bock, Wolfgang; Braun, Jürgen; Busch, Christian; Buss, Wolfgang; Dresel, Wilfried; Freiler, Carmen; Harperscheid, Manfred; Heckler, Rolf-Peter; Hörner, Dietrich; Kubicki, Franz; Lingg, Georg; Losch, Achim; Luther, Rolf; Mang, Theo; Noll, Siegfried; Omeis, Jürgen (2003). "Lubricants and Lubrication". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a15_423. ISBN   3-527-30673-0.
  8. Groen, Karin (2003). "Pigment". Grove Art Online . Oxford University Press. doi:10.1093/gao/9781884446054.article.T067586. ISBN   978-1-884446-05-4 . Retrieved January 16, 2018.
  9. 1 2 3 4 5 Centeno, Silvia A.; Mahon, Dorothy (Summer 2009). Leona, Marco (ed.). "The Chemistry of Aging in Oil Paintings: Metal Soaps and Visual Changes". The Metropolitan Museum of Art Bulletin. Metropolitan Museum of Art. 67 (1): 12–19. JSTOR   40588562. PDF of full issue.
  10. Fleury, Paul (1912). "Manufacture and Different Treatments of White Zinc, its Modifications and Improvements". The Preparation and Uses of White Zinc Paints (1st ed.). London: Scott, Greenwood & Son. pp. 122–154. ... and although Petit declares this theory false, it is none the less on it and on its data that he bases his system of manufacture of hydrated white zinc, of which he is the inventor that is to say, the saponification of the oil, or the formation of metallic salts, dissolved therein.