FIXED OILS AND FATS

Lipids:
Lipids are organic compounds that are found in living organisms. They have variety of structures and
functions, and soluble in organic solvents due to their hydrocarbon component.
Lipids are oily substances that have poor solubility in water. There are four types of lipids:
(i) Mineral oils :Oils from under the earth’s crust such as petroleum and kerosene
(ii) Essential Oils: Of plant origin and have a pleasant smell such as lemon oil. Mainly contains
isoprenoids.
(iii) Oils and Fats: These are esters of glycerol with higher fatty acids and are also called tri
glycerides
(iv) Waxes: These are mixtures of esters of higher fatty acids with higher monohydric
alcohols(in contrast to glycerol I fixed oils)Eg: bees wax contains myricylpalmitate.

FatsandOils

Fats and oils are composed of molecules known as triglycerides, which are esters composed
ofthreefattyacid unitslinked toglycerol [1,2].

Fats and oils are called triglycerides because they are esters composed of three fatty acid
unitsjoinedtoglycerol,a trihydroxyalcohol:

If all threeOH groups on theglycerolmolecule are esterified with the same fatty acid,
theresultingesteriscalledasimpletriglyceride.Althoughsimpletriglycerideshavebeensynthesized in
the laboratory, they rarely occur in nature. Instead, a typical triglyceride obtainedfrom naturally
occurring fats and oils contains two or three different fatty acid components and isthustermeda
mixedtriglyceride.

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A triglyceride is calleda fat if it is a solid at 25°C; it is called oil if it is a liquid at thattemperature.
These differences in melting points reflect differences in the degree of unsaturationand number of
carbon atoms in the constituent fatty acids. Triglycerides obtained from
animalsourcesareusuallysolids,whilethoseofplantoriginaregenerallyoils.Therefore,wecommonlyspe
akofanimalfatsandvegetableoils.

Saturated fats canstack themselves in a closely packedarrangement, sothey cansolidify easilyand

are typically solid at room temperature. For example, animal fats tallow and lard are high
insaturatedfattyacidcontentandaresolids.Oliveandlinseedoilsontheotherhandareunsaturated and
liquid. Fats serve both as energy sources for the body, and as stores for energy inexcess of what
the body needs immediately. Fats are broken down in the healthy body to releasetheir
constituents,glycerol and fatty acids. Glycerolitself can beconverted toglucoseby theliverand
sobecome asourceofenergy.

Differentiatebetweenfatsandoils
Fats Oils
1. Fats are solids or semisolids at room Oilsareliquidsatroomtemperature
Temperature
2. Fatscontainslargeamountofsaturatedfatty Oilscontainslargeamountofunsaturated
acidse.g.stearicandpalmiticacids fattyacidse.g.oleicacid
3. Fatsmeltathightemperature Meltatlowtemperature
4. Fatsdonotcontaindoublebonds Oilshavedoublebonds
5. Fatsaremorestable Oilsarelessstable
6. Fatsareanimalfats Oilsarevegetablefats

Physical Properties of Fats and Oils

Pure fats and oils are colorless, odorless, and tasteless. The characteristic colors,odors, andflavors
that we associate with some of them are imparted by foreign substances that are lipidsoluble and
have been absorbed by these lipids. For example, the yellow color of butter is due tothe presence
of the pigment carotene; the taste of butter comes from two compounds diacetyl and3-hydroxy-2-
butanone produced by bacteria in the ripening cream from which the butter is made.

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Fatsandoilsarelighterthanwater,havingdensitiesofabout0.8g/
cm3.Theyarepoorconductorsofheatandelectricityandthereforeserveasexcellentinsulatorsforthebody,
slowingthelossofheatthroughtheskin.

Chemicalstructure

There are many different kinds of fats, but each is a variation on the same chemical structure.
Allfats are derivatives of fatty acids and glycerol. Most fats are glycerides,particularly
triglycerides (triesters of glycerol). One chain of fatty acid is bonded to each of thethree -OH
groups of the glycerol by the reaction of the carboxyl end of the fatty acid (-
COOH)withthealcohol;i.e.threechainspermolecule.Wateriseliminatedandthecarbonsarelinkedby an
-O- bond through dehydration synthesis. This process is called esterification and fats aretherefore
esters.Asasimplevisualillustration,ifthekinksand angles ofthesechainswerestraightened out, the
molecule would have the shape of a capital letter E. The fatty acids
wouldeachbeahorizontalline;theglycerol"backbone"wouldbetheverticallinethatjoinsthehorizontalli
nes.Fatstherefore have"ester"bonds.

The properties of any specific fat molecule depend on the particular fatty acids that constitute
it.Fatty acidsforma family ofcompoundsthatarecomposed ofincreasing numbers of
carbonatomslinkedintoazig-zagchain(hydrogenatomstotheside).Themorecarbonatomstherearein
any fatty acid, the longer its chain will be. Long chains are more susceptible to
intermolecularforces of attraction (in this case, van der Waals forces), and so the longer ones melt
at a highertemperature(meltingpoint).

Fig.Structure of a triglyceride and saturated, monounsaturated and polyunsaturated

fattyacids.
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Fatty acids are classified according to the presence and number of double bonds in their
carbonchain. Saturated fattyacids(SFA)containnodoublebonds, monounsaturated
fattyacids(MUFA)containone,and polyunsaturated fatty acids(PUFA)containmorethanone
doublebond. Bothlength andsaturation of fatty acidsaffectthe arrangement of the membrane in
ourbody cells andthereby its fluidity.Shorterchainfatty acidsand ones with greater unsaturationare
less stiff and less viscous, making the membranes more flexible. This influences a range
ofimportantbiologicalfunctions.

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Importanceforlivingorganisms

Fats are also sources of essential fatty acids, an important dietary requirement. They
provideenergy as noted above.Vitamins A, D, E, and K are fat-soluble, meaning they can only
bedigested, absorbed, and transported in conjunction with fats. Fats play a vital role in
maintaininghealthy skin and hair, insulating body organs against shock, maintaining body
temperature, andpromotinghealthy cellfunction.Fat alsoservesasa usefulbuffer
againstahostofdiseases.Whenaparticularsubstance,whetherchemicalorbiotic,reachesunsafelevelsint
hebloodstream, the body can effectively dilute or at least maintain equilibrium of the
offendingsubstancesbystoringitinnewfattissue.Thishelpstoprotectvitalorgans,untilsuchtimeasthe

offending substances can be metabolized or removed from the body by such means as
excretion,urination,accidentalorintentionalbloodletting,sebumexcretion,andhairgrowth.

Physical Characteristics of Fats and Oils:

They are

• Colorless liquid or solid, but maybe yellow or brown due to impurities.

• Lighter than water and immiscible with it

• Soluble in organic solvents such as petroleum ether, benzene etc.

• Non-volatile

• Upon heating they decompose to give an irritating odor

• Form emulsions in the presence of detergents/surfactants

Various chemical reactions of fats and oils

1. Hydrolysis

Thehydrolysisoffatsandoilsinthepresenceofabasemakessoapandisknownassaponification. Double
bonds present in unsaturated triglycerides can be hydrogenated to convertoils (liquid)
intomargarine (solid).

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Hydrolysis can also be done by heating fat with water under pressure. Alkaline hydrolysis of
fatsproducessaltsoffattyacidscalledassoapsandhencethisreactionisalsoknownassaponification.Com
monsoapsare the mixtureof sodium saltsof‘C’atoms(12 atoms) andhigher fatty acids. Soap
molecules have both lipophillic (lipid loving) and hydrophilic (waterloving)group. The
lipophillicgroupdissolvesoils whilehydrophilic portion dissolves
water.Soapmoleculesondissolutioninwaterformsmicelle.Hydrolysiscanbedoneinthreeways-

a) Hydrolysisbywater:Fatsundergoeshydrolysisinpresenceofwaterat443Kand6-8atmospheric
pressure.Zincoxideisused ascatalyst.

b) Hydrolysisbyenzymes:hydrolysis of fats and oils can be done by adding enzyme lipase toan
emulsion of fatinwater.

c) Hydrolysisbyacids:mineral acids cause hydrolysis of fats. For this mixture of sulphonicacids

whichareobtainedbysulphonationofmixtureofoleicacidandbenzene.

The above three ways gives glycerol and fatty acids as a product of hydrolysis of fats
whilealkalinehydrolysisoffatsgivesglycerolandsoapwhichareusedascleansingagent.Thecleansingpr
opertyofsoapdependsupontheabilitytoformemulsionwithfatsolublematerials.

2. Hydrogenation

Oils have largeamountof unsaturated portionin the form of glycerides.When hydrogen ispassed
through oils under pressure and by using catalyst at high temperature oils gets convertedinto solid
fats. This process is known as hardeningofoils. By hydrogenation, unsaturated acidpart of oil gets
reduced into saturated part and hence liquid oil gets converted into semi-solid fat.Hydrogenation is
carriedout in a closed container inthe presence of finely powdered catalyst(0.05 - 0.2% of nickel)
at temperature as high as 150-200oC. The catalyst is usually removed byfiltration. During
hydrogenation process a proportion of the cis double bonds are isomerized totrans double bonds
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and there is also migration of double bonds. The hydrogenation process hasmade it possible to
extend the food uses of a number of vegetable oils and marine oils whosemeltingpointsaretoolow.

3. Hydrogenolysis:

This is a cleavage reaction in which fat or oil molecule is treated with excess of hydrogen
underpressure in presence of copper-chromium catalyst. In this reaction fat or oil gets splits up
intoglyceroland higheraliphaticalcohols.

4. Saponification:

Saponification is a process that involvesconversion of fat, oil or lipid into soap and glycerol
bytheactionofheatinthepresenceofaqueousalkali(e.g.NaOH).Soapsaresaltsoffattyacidsand fatty
acids are monocarboxylic acids that have long carbon chains (at least 10) e.g. sodiumpalmitate.

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5. Rancidification:

Rancidification is the process of complete or incomplete oxidation or hydrolysis of fats and

oilswhen exposed to air, light, or moisture or by bacterial action, resulting
inunpleasanttasteandodor. Rancidity reactions may be due to hydrolysis of ester bonds (hydrolytic
rancidity) or due
tooxidationofunsaturatedfattyacids(oxidativerancidity).Rancidityoccursbythefollowingways-

a) Oxidation of unsaturated fatty acids: in presence of light and moisture, small amount
ofunsaturated acids present in fats/oils gets oxidized by air to form peroxides which further
breakdown into aldehydes having unpleasant smell and taste. Saturated fatty acids do not get
rancid.This problem can bechecked by adding smallquantity of phenolic substances which act
asantioxidant.

b) Enzymatichydrolysis:Duetopresenceofmicro-organismsfatsgetshydrolyzedbyenzymesto
produce fatty acids having sour taste and unpleasant odour. For example butter gets rancid dueto
productionofbutyricacid inthismanner.

c) β-oxidationofsaturatedfattyacids:fatshavingsaturatedfattyacidsundergoketonerancidity.
Saturated acids undergo β-oxidation to form keto acids which gives carbon dioxide
toformketoneshavingunpleasantodour.

6. Dryingoils:

A drying oil is the oil that hardens to a tough, solid film after a period of exposure to air. The
oilhardensthroughachemicalreactioninwhichthecomponentscrosslink(andhence,polymerize)bythea
ctionofoxygen(notthroughtheevaporationofwaterorothersolvents).Dryingoilsarea key component
of oilpaint and some varnishes.Some commonly used drying oils includelinseed oil, tung oil,
poppy seed oil, perilla oil, and walnut oil. Drying oils (wild rose oil, linseedoil, wheat oil) contain
more than 50% of polyunsaturated acids. They are quickly absorbed
andleavenogreasylayeronoilyskin.Theirlightconsistencymakesthemagoodmake-upprimer.

The"drying",hardening,or,moreproperly,curing ofoilsistheresultofautoxidation,theaddition of
oxygen to an organic compound and the subsequent crosslinking. This process begins with an
oxygen molecule (O2) in the air inserting into carbon-hydrogen (C-H) bonds adjacent to one of the
doublebonds within the unsaturatedfatty acid. Theresulting hydroperoxides
aresusceptibletocrosslinkingreactions.Bondsformbetweenneighboringfattyacidchains,resulting in a
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polymer network, often visible by formation of a skin-like film on samples.
Thispolymerizationresultsinstablefilmsthat,whilesomewhatelastic,donotflowordeformreadily.
Diene-containing fatty acid derivatives, such as those derived from linoleic acid,
areespeciallypronetothisreactionbecausetheygeneratepentadienylradicals.Monounsaturated

fattyacids,suchasoleicacid,areslowertoundergodryingbecausetheallylicradicalintermediates are less

stable.

Oilsdependingupontheirexposuretolightandaircanbeclassifiedas-

a) Non-dryingoils:Theseoilsonexposuretolightandlongstoragegetrancid.Oilsgetdecomposed into
glycerol and fatty acids (saturated and unsaturated). The unsaturated acids
getsoxidisedintoaldehydesandacidswithlessercarbonatomsinthemolecule.Thesaturatedacidsget
decomposed by enzymes to form ketones. For example olive oil, almond oil, Babassu
oil,Baobaboil,Coconut oil,PeanutoilandTigerNutOil.

b) Drying oils: They form a solid elastic film. A good drying oil dries within 4-5 hours.
ForexampleLinseed oil.

c) Semi-drying oils:It is the oil which partially hardens when exposed to air. This is as opposedto
a drying oil, which hardens completely, or a non-drying oil, which does not harden at all. Oilswith
an iodine number of 115-130are considered semi-drying.Semi-drying oilscontain20%-50% of
polyunsaturated acids. They include: sweet almond oil, apricot seed oil, Cottonseed
oil,SesameoilandGrapeseedoil.

Analysisoffatsandoil
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Purity and composition of oil depends upon the degree of unsaturation, acidity on hydrolysis,
anditsmolecularweight.Avarietyofphysicaltestshavebeenperformedonfatsandoilstodetermine their
composition and quality. Some of the common tests are as follows and these testsarealsoknownas
analytical constants.

a) Acid value: The Acid value is defined as the number of milligrams of potassium hydroxide
(KOH) required to neutralize the free fatty acids present in one gram of the substance(fatsoroil).

Procedure: Weigh about 10g of the substance being examined, in an iodine flask. Prepare
50mlmixture of equal volumes of ethanol (95 per cent) and ether, add 0.5 ml phenolphthalein
solutionandtitrateitagainst0.1Naqueouspotassiumhydroxide(KOH)solutionuntilthesolution remains
faintly pink after shaking for 30 seconds. Calculate the acid value from the followingequation.

Acidvalue= 56.01 x T.V x N / W

Where, T.V= Volume of potassium hydroxide solution used (ml)

N = Normality of KOH solution used

W=theweightofthefatoroilbeingexamined(gm).

Significance: Acid value indicates the degree of rancidity of the given fat. High acid values
ariseinrancifiedoils.Rancidificationisthe decomposition offatsandotherlipidsby hydrolysisand/or
oxidation. Oxidation primarily occurs with unsaturated fats by a free radical-mediatedprocess,
which is responsible for producing the unpleasant and obnoxious odours and
flavours.Rancidification can be reduced (but not completely eliminated) by storing the fats and
oils at lowtemperatureandawayfrom light.

b) Saponificationvalue:Saponificationvalueisdefinedasthenumberofmilligramsofpotassiumhydro
xide required tocompletelysaponifyonegramoffatoroil.i.e the number of mg of KOH required to
neutralize the free fatty acids and the fatty acids obtained by hydrolysis of esters present in one
gram of fixed oil or fat.

Procedure: Weigh about 2 g of the substance being examined in an iodine flask with
reflexcondenser.Add 25 mlof 0.5 ethanolic potassium hydroxide solution and boil under
refluxonwater bath for 30 minutes. Remove the condenser and add 1 ml of phenolphthalein
solution andtitrate immediately with 0.5 M Hydrochloric acid. Note the reading as ‘A’. Repeat the
operationomitting thesubstance being examined.Notethe reading as‘B’.Calculate
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thesaponificationvalue fromthefollowing equation,

Saponificationvalue=28.05×(B-A)/

WWhere,W=weightofsubstance(gm).B=

mlof HClusedforblanktitration

A=mlof0.5NHClusedfortitration

Significance:Thesaponificationvalueisusedprimarilyasanidentificationaidtodetectsadulteration
with unsaponifiable matter. It is also used to determine the extent of
compounding(fatsandoilsaddedtoimproveoiliness)inalubricant.

c) Ester value: The Ester value is the number of milligrams of potassium hydroxide required
toreact with esters present in 1 g of fat or oil. The difference between saponification value and
acidvalue is calledEstervalue.

Estervalue=Saponificationvalue–Acidvalue

d) Iodine value: Iodine value is defined as the number of grams of iodine taken up by 100 gm
offatoroiloritisthenumberofgramsofiodinewhichwillcombinewith100gmofthefatoroil.
1) Hubl’smethod: Fat or oil sample is dissolved in carbon tetrachloride and is treated withexcess
of standard solution of ethanolic iodine in presence of mercuric chloride. Unused iodine
isthencalculated bytitrationwithstandard sodiumthiosulphatesolution.

2) Wij’s method: This method uses iodine monochloride in acetic acid in presence of
iodine.Iodinemonochloridereadilycombineswiththedoublebondspresentinfatandoil.Theunreacted
iodine is then calculated by the addition of potassium iodide and titration with standardsolution
ofsodiumthiosulphsteusingstarchasindicator.

CalculatetheIodinevaluefromthefollowingequation:

Iodine value = 1. 269 ×

(b-a)/WWhere,W=weighoffatoroiltak

en.
b = reading of actual
titrationa=readingofblanktitra
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 tion
Significance:Iodinevaluegivesusanideaabouttheproportionofunsaturatedfattyacidspresentsbothinfr
eeandcombinedformsofesters.Susceptibilityofrancidityincreasesfortheoilsorfatshavinghigheriodine
values.Iodinevaluehelpstoindicatethecompositionofcomplex mixture, as well as pure substances. It
may be determined by any of the followingmethods.

e) Acetyl value: It is defined as the number of milligrams of potassium hydroxide required

toneutralise acetic acid produced by the saponification of one gram of completely acetylated fat
oroil.Ithelps indetermining the numberof alcoholicgroupspresentinoilorfat.

Procedure:

Determine the saponification value of the sample first.

Next acetylate the sample by the following method:

Place 10gms of the sample with 20ml of acetic anhydride in a 200ml RBF attached to a reflux
condenser. Boil gently for 2hrs, allow to cool, add 600ml of water and transfer to a separating
funnel. Discard the lower layer and wash the acetylated product with three or more quantities, each
of 50ml of warm NaOH until the washings are no longer acidic to litmus. Finally shake with 20ml
of water and remove the aqueous layer as completely as possible. Determine the saponification
value off the acetylated substance.

Acetyl value = 1335 (b-a) / (1335 –a)

a = saponification value of substance

b = saponification value of acetylated substance.

f) Reichert-MeisslValue(R.M.Value):Itisdefinedasthenumberofmlof0.1NKOHsolution required
to neutralise the water soluble steam or to neutralise the distillate of 5 gm ofhydrolysed fat or oil.
It is an indicator of how much volatile fatty acid can be extracted from fatthrough saponification.
It is a measure of the volatile fatty acid residues present in a given fat oroil.
Procedure:Tothe10gmofsampleaddanexcessof0.1NNaOHsolutioninordertocompletely saponify
the fat. The solution is then acidified with dil.H 2SO4 and is undergo steamdistillation.
Thedistillatecontaining the volatileacid isthen titrated with0.1N KOHsolutionusingphenolphthalein
asan indicator.
R.M.value=1.10(T1-T2)
Where,T1=volumeof0.1NKOHusedforthetitrationT2=volu

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 meof0.1NKOHusedforblanktitration
Significance: R.M. value is useful for testing the purity of the butter and desi ghee which
maycontainahighamountofglyceridesofbutyricacidandothersteamvolatilefattyacidresidues.Fore.g.A
dulteratedbutterhaslowR.M.valuethanthatofpurebutter.ThisR.M.valuenumberis an indicator of
non-fat compounds inediblefatslike butter andghee. Hence,it helps
indeterminingthepurityofgheeandbutter.

Uses of Oils and Fats

• Many oils and fats are used as food material.
• Oils and fats are used for the manufacture of glycerol, fatty acids, soaps, candles, vegetable ghee,
margarine, hair oils, etc.
• Oils like linseed oil, tung oil, etc., are used for the creation of paints, varnish, etc.
• Castor oil is used as purgative and codliver oil as a source of vitamins A and D. Almond oil is used in
pharmacy. Olive oil is also used as medicine.
• Oils are also used as illuminants and lubricants.

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