Constants of Fats,
Fatty Oils, Waxes,
Balsams, Resins, etc.
Chapter 13
OBJECTIVES
At the end of the lesson, the student is able to:
• Define fat constants (e.g. acid value, saponification value,
ester value, iodine value, acetyl value and hydroxyl value)
• Perform calculations associated with each constant
• Explain the relevance of performing assays in fats, waxes and
oils
LIPIDS
FIXED OILS FATS WAXES
Long chain fatty acid + Long chain fatty acid + Long chain fatty acid + high
glycerol glycerol molecular weight alcohol
From vegetables From plants From plants and animals
Liquid @ room temperature Solid @ room temperature Semisolid
Examples: Cottonseed oil, Example: Cod liver oil (fish Examples: Beeswax,
coconut oil, castor oil oil) Carnauba wax
ACID VALUE
• Also known as acid number or acidity index.
• Is defined as the number of milligrams of potassium
hydroxide (KOH) necessary to neutralize the free fatty acids
in 1 g of oil, fat, wax, resin, balsam or similar organic
substance of complex composition.
• Acid value: N x V x 56.11 mg/mEq / weight in g
ACID VALUE
• As a rule, fresh or recently prepared fatty substances contain
little or no free acids.
• Upon aging, the acid value increases, especially if the
substance is not well protected from the simultaneous action
of light and air.
• Acid value is a measure of rancidity (not necessarily an
indication because it is the result of the action of air, bacteria
or liberated fatty acids); could be a measure of adulteration.
ACID VALUE
Sample problem:
If a 2-gram sample of cod-liver oil required 4.5 mL of
0.02 N NaOH in the titration of the free fatty acids, would the
oil conform with the official purity requirement? What would
be the acid number of the oil?
SAPONIFICATION VALUE
• Also referred to as saponification number, or Koettsdorfer
number.
• Is defined as the number of milligrams of potassium
hydroxide (KOH) necessary to neutralize the free fatty acids
and saponify the esters in 1 g of oil, fat, wax, resin, balsam or
similar organic substance of complex composition.
SAPONIFICATION VALUE
• Involves a blank determination
• Saponification value:
(Blank – actual) x N x 56.11 mg/mEq / wt of sample (g)
*If both acid value and ester value is already given:
SV = AV __ EV
SAPONIFICATION VALUE
Sample problem:
A sample of corn oil weighing 1.600 g saponified with 25
mL of 0.4 N KOH required 9.0 mL of 0.5 N HCl to titrate the
excess KOH. In the blank determination, 20 mL of 0.5 N HCl
was required to titrate the alkali. Calculate the saponification
value of the sample.
ESTER VALUE
• Also known as ester number
• Is defined as the number of milligrams of potassium
hydroxide (KOH) required to saponify the esters in 1 g of fatty
or volatile oil, fat, wax, resin, balsam or similar organic
substance of complex composition.
• Ester value: Saponification value – acid value
ESTER VALUE
• Used, in particular, in the analysis of yellow and white wax,
since it serves to indicate the presence of adulterants, such
as paraffin.
• Official substances with the required ester values:
• White wax – 72 to 79
• Yellow wax – 72 to 77
IODINE VALUE
• Also referred to as iodine number
• Is the number of grams of iodine absorbed under specified
conditions by 100 g of oil, fat, wax or other substance.
• Measure of the degree of unsaturation (proportion of
unsaturated fatty acids present, that has the property of
absorbing iodine).
IODINE VALUE
• Determination of iodine number of fats and oils is important
since it serves to characterize them and to indicate whether
they are pure or admixtures.
Drying oils >120 Linseed oil and Cod liver oil (fish oil)
Non-drying oils <100 Olive oil and almond oil
Semi-drying oils 100-120 Cottonseed oil and sesame oil
IODINE VALUE
• Determination of iodine number is useful in the following:
• Serves to indicate in a definite manner the class to which an unknown fat or
oil belongs.
• Serves as a means of detecting adulteration
• Several methods for determining the iodine number:
• Method I: Hanus method (use of I2 and Br2 in glacial acetic acid)
• Method II: Wij’s method (USP method)
• Method III: Hubl’s method (unofficial method)
IODINE VALUE
Iodine value:
[(Blank – actual) x N x 0.1269 g/mEq / wt in g] x 100
HYDROXYL VALUE
• Also referred to as the hydroxyl value or hydroxyl number
• Is the number of milligrams of potassium hydroxide (KOH)
equivalent to the hydroxyl content of 1 g of the substance.
• Indication of the identity and purity of fatty substances
possessing alcoholic hydroxyl groups.
• HV is inversely proportional to the MW
ACETYL VALUE
• Correspond closely to the hydroxyl value of fatty alcohols.
• Defined as the number of milligrams of potassium hydroxide
(KOH) required to neutralize the acetic acid obtained by
saponification of 1 g of acetylated fatty acids.
