Saponification value or saponification number (SV or SN) represents the number of milligrams of
potassium hydroxide
Potassium hydroxide is an inorganic compound with the formula K OH, and is commonly called caustic potash.
Along with sodium hydroxide (NaOH), KOH is a prototypical strong base. It has many industrial and niche applications, most of which exp ...
(KOH) or
sodium hydroxide (NaOH) required to
saponify one gram of
fat
In nutrition, biology, and chemistry, fat usually means any ester of fatty acids, or a mixture of such compounds, most commonly those that occur in living beings or in food.
The term often refers specifically to triglycerides (triple est ...
under the conditions specified.
It is a measure of the average
molecular weight
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
(or chain length) of all the
fatty acid
In chemistry, particularly in biochemistry, a fatty acid is a carboxylic acid with an aliphatic chain, which is either saturated or unsaturated. Most naturally occurring fatty acids have an unbranched chain of an even number of carbon atoms, ...
s present in the sample in form of
triglyceride
A triglyceride (TG, triacylglycerol, TAG, or triacylglyceride) is an ester derived from glycerol and three fatty acids (from ''wikt:tri-#Prefix, tri-'' and ''glyceride'').
Triglycerides are the main constituents of body fat in humans and other ...
s. 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 (such as coconut and palm oil) are more suitable for
soap
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 use ...
making.
Determination
To determine saponification value, the sample is treated with an excess of
alkali (usually an
ethanol
Ethanol (abbr. EtOH; also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound. It is an alcohol with the chemical formula . Its formula can be also written as or (an ethyl group linked to a ...
ic solution of potassium hydroxide) for half an hour under
reflux
Reflux is a technique involving the condensation of vapors and the return of this condensate to the system from which it originated. It is used in industrial and laboratory distillations. It is also used in chemistry to supply energy to reactions ...
. The KOH is consumed by reaction with triglycerides, which consume two equivalents of base.
Diglyceride
A diglyceride, or diacylglycerol (DAG), is a glyceride consisting of two fatty acid chains covalently bonded to a glycerol molecule through ester linkages. Two possible forms exist, 1,2-diacylglycerols and 1,3-diacylglycerols. DAGs can act as su ...
s consume two equivalents of KOH.
Monoglyceride
Monoglycerides (also: acylglycerols or monoacylglycerols) are a class of glycerides which are composed of a molecule of glycerol linked to a fatty acid via an ester bond. As glycerol contains both primary and secondary alcohol groups two differen ...
s and free fatty acids, as well as by other esters such as
lactone
Lactones are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-one structure (), or analogues having unsaturation or heteroatoms replacing one or more carbon atoms of the ring.
Lactones are formed by intramolecular esterification of the co ...
s consume one equivalent of base
At the end of the reaction the quantity of KOH is determined by
titrated
Titration (also known as titrimetry and volumetric analysis) is a common laboratory method of quantitative chemical analysis to determine the concentration of an identified analyte (a substance to be analyzed). A reagent, termed the ''titrant'' ...
using standard solution of
hydrochloric acid
Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid
Acid strength is the tendency of an acid, symbol ...
(HCl). Key to the method is the use of
phenolphthalein
Phenolphthalein ( ) is a chemical compound with the formula C20 H14 O4 and is often written as "HIn", "HPh", "phph" or simply "Ph" in shorthand notation. Phenolphthalein is often used as an indicator in acid–base titrations. For this applica ...
indicator, which indicates the consumption of strong base (KOH) by the acid, not the weak base (potassium carboxylates). The SV (mg KOH/ g of sample) is calculated as following:
:where:
:
is the volume of HCl solution used for the blank run, in mL;
:
is the volume of HCl solution used for the tested sample, in mL;
:
is the
molarity
Molar concentration (also called molarity, amount concentration or substance concentration) is a measure of the concentration of a chemical species, in particular of a solute in a solution, in terms of amount of substance per unit volume of solu ...
of HCl solution, in mol / L;
: is the molecular weight of KOH, in g / mol;
:
is the weight of sample, in g.
For example, standard methods for determination of SV of vegetable and animal fats are as follows:
The SV can also be calculated from the fatty acid composition as determined by
gas chromatography (
AOCS Cd 3a-94).
Handmade
soap makers who aim for
bar soap use
sodium hydroxide (NaOH), commonly known as
lye
A lye is a metal hydroxide traditionally obtained by leaching wood ashes, or a strong alkali which is highly soluble in water producing caustic basic solutions. "Lye" most commonly refers to sodium hydroxide (NaOH), but historically has been u ...
, rather than KOH (caustic potash) which produces soft paste, gel or liquid soaps. In order to calculate the lye amount needed to make bar soap, KOH values of SV can be converted to NaOH values by dividing KOH values by the ratio of the molecular weights of KOH and NaOH (1.403).
Calculation of average molecular weight of fats and oils
The theoretical SV of a pure triglyceride molecule can be calculated by the following equation (where MW is its molecular weight):
:where:
:3 is the number of fatty acids residues per triglyceride
:1000 is the conversion factor for milligrams to grams
:56.1 is the molar mass of KOH.
For instance,
triolein
Triolein is a symmetrical triglyceride derived from glycerol and three units of the unsaturated fatty acid oleic acid. Most triglycerides are unsymmetrical, being derived from mixtures of fatty acids. Triolein represents 4–30% of olive oil.
Tr ...
, a triglyceride occurring in many fats and oils, has three
oleic acid
Oleic acid is a fatty acid that occurs naturally in various animal and vegetable fats and oils. It is an odorless, colorless oil, although commercial samples may be yellowish. In chemical terms, oleic acid is classified as a monounsaturated omeg ...
residues esterified to a molecule of
glycerol
Glycerol (), also called glycerine in British English and glycerin in American English, is a simple triol compound. It is a colorless, odorless, viscous liquid that is sweet-tasting and non-toxic. The glycerol backbone is found in lipids known ...
with a total MW of 885.4 (g / mol). Therefore, its SV equals 190 mg KOH / g sample.
In comparison, trilaurin with three shorter fatty acid residues (
lauric acid
Lauric acid, systematically dodecanoic acid, is a saturated fatty acid with a 12-carbon atom chain, thus having many properties of medium-chain fatty acids. It is a bright white, powdery solid with a faint odor of bay oil or soap. The salts and ...
) has a MW of 639 and an SV of 263.
As it can be seen from equation (2), the SV of a given fat is inversely proportional to its molecular weight. Actually, as fats and oils contain a mix of different triglycerides species, the average MW can be calculated according to the following relation:
This means that
coconut oil with an abundance of medium chain fatty acids (mainly lauric acid) contain more fatty acids per unit of weight than, for example,
olive oil (mainly oleic acid). Consequently, more
ester
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides a ...
saponifiable functions were present per g of coconut oil, which means more KOH is required to saponify the same amount of matter, and thus a higher SV.
The calculated molecular weight (Eq. 3) is not applicable to fats and oils containing high amounts of unsaponifiable material, free fatty acids (> 0.1%), or
mono-
Numeral or number prefixes are prefixes derived from numerals or occasionally other numbers. In English and many other languages, they are used to coin numerous series of words. For example:
* unicycle, bicycle, tricycle (1-cycle, 2-cycle, 3-cy ...
and
diacylglycerols (> 0.1%).
Unsaponifiables
Unsaponifiables are components of a fatty substance (
oil
An oil is any nonpolar chemical substance that is composed primarily of hydrocarbons and is hydrophobic (does not mix with water) & lipophilic (mixes with other oils). Oils are usually flammable and surface active. Most oils are unsaturated ...
,
fat
In nutrition, biology, and chemistry, fat usually means any ester of fatty acids, or a mixture of such compounds, most commonly those that occur in living beings or in food.
The term often refers specifically to triglycerides (triple est ...
,
wax
Waxes are a diverse class of organic compounds that are lipophilic, malleable solids near ambient temperatures. They include higher alkanes and lipids, typically with melting points above about 40 °C (104 °F), melting to giv ...
) that fail to form
soap
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 use ...
s when treated with alkali and remain insoluble in water but soluble in organic solvents. For instance, typical
soybean oil
Soybean oil (British English: soyabean oil) is a vegetable oil extracted from the seeds of the soybean (''Glycine max''). It is one of the most widely consumed cooking oils and the second most consumed vegetable oil. As a drying oil, processed s ...
contains, by weight, 1.5 – 2.5% of unsaponifiable matter. Unsaponifiables include nonvolatile components :
alkanes,
sterols,
triterpene
Triterpenes are a class of chemical compounds composed of three terpene units with the molecular formula C30H48; they may also be thought of as consisting of six isoprene units. Animals, plants and fungi all produce triterpenes, including squa ...
s,
fatty alcohols,
tocopherol
Tocopherols (; TCP) are a class of organic chemical compounds (more precisely, various methylated phenols), many of which have vitamin E activity. Because the vitamin activity was first identified in 1936 from a dietary fertility factor in rat ...
s and
carotenoids as well as those that mainly result from the saponification of
fatty esters (sterols esters, wax esters, tocopherols esters, ...). This fraction may also contain environmental contaminants and residues of
plasticizer
A plasticizer ( UK: plasticiser) is a substance that is added to a material to make it softer and more flexible, to increase its plasticity, to decrease its viscosity, and/or to decrease friction during its handling in manufacture.
Plasticiz ...
s,
pesticides,
mineral oil
Mineral oil is any of various colorless, odorless, light mixtures of higher alkanes from a mineral source, particularly a distillate of petroleum, as distinct from usually edible vegetable oils.
The name 'mineral oil' by itself is imprecise, ...
hydrocarbons and aromatics.
Unsaponifiable constituents are an important consideration when selecting oil mixtures for the manufacture of soaps. Unsaponifiables can be beneficial to a soap formula because they may have properties such as
moisturization,
conditioning,
antioxidant, texturing etc. On the other hand, when proportion of unsaponifiables is too high (> 3%), or the specific unsaponifiables present do not provide significant benefits, a defective or inferior soap product can result. For example,
shark oil is not suitable for soap making as it may contain more than 10% of unsaponifiable matter.
For edible oils, the tolerated limit of unsaponifiable matter is 1.5% (olive, refined soybean), while inferior quality crude or
pomace
Pomace ( ), or marc (; from French ''marc'' ), is the solid remains of grapes, olives, or other fruit after pressing for juice or oil. It contains the skins, pulp, seeds, and stems of the fruit.
Grape pomace has traditionally been used to pro ...
oil could reach 3%.
Determination of unsaponifiables involves a saponification step of the sample followed by extraction of the unsaponifiable using an organic solvent (i.e.
diethyl ether
Diethyl ether, or simply ether, is an organic compound in the ether class with the formula , sometimes abbreviated as (see Pseudoelement symbols). It is a colourless, highly volatile, sweet-smelling ("ethereal odour"), extremely flammable li ...
). Official methods for animal and vegetable fats and oils are described by
ASTM D1065 - 18,
ISO
ISO is the most common abbreviation for the International Organization for Standardization.
ISO or Iso may also refer to: Business and finance
* Iso (supermarket), a chain of Danish supermarkets incorporated into the SuperBest chain in 2007
* Iso ...
3596: 2000 or 18609: 2000,
AOCS method Ca 6a-40.
Saponification values and unsaponifiables of various oils and fats
See also
*
*
*
*
*
*
*
*
*
*
Soapmaking
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 a ...
— Small scale process of producing soap
References
{{reflist
Analytical chemistry