LIPID

Soluble in non-polar solvents and insoluble in polar

solvents. Lipid is not polymers.

Lipids:
1. Fatty acids
2. Neutral fats and oils
3. Waxes
4. Phospholipid
5. Sterols
6. Fat soluble vitamins
Fatty Acids

O
R C OH

#1 Carbon Acid Group

O
R C OH Polar End - Hydrophilic End

Non-polar End - Hydrophobic End

(Fat-soluble tail)
 Saturated Fatty Acids

O
8 7 6 5 4 3 2 1
CH3 CH2 CH2 CH2 CH2 CH2 CH2 C OH

Octanoic Acid
 Unsaturated Fatty Acids
O
8 7 6 5 4 3 2 1
CH3 CH2 CH2 CH2 CH2 CH2 CH2 C OH
3 - Octenoic Acid
O
8 7 6 5 4 3 2 1
CH3 CH2 CH2 CH2 CH2 CH2 CH2 C OH
3, 6 - Octadienoic Acid

Short hand: 8:1 (D3)

8:2 (D3,6)
 Cis And Trans Fatty Acids

H H O
CH3 (CH2 )7 C C (CH2 )7 C OH
10 9
Cis 9 - Octadecenoic Acid (oleic)
H O
CH3 (CH2 )7 C C (CH2 )7 C OH
H
Trans 9 - Octadecenoic Acid (elaidic acid)
 Polyunsaturated Fatty Acids

Linoleic acid: Cis, cis, 9, 12 - Octadecadienoic acid

Linolenic acid: Cis, cis, cis 9, 12, 15 - Octadecatrienoic acid
Arachidonic acid: Cis, cis, cis, cis 5, 8, 11, 14 - Eicosatetraenoic
acid
 Naturally-occurring fatty acids

O
R CH2 CH CH CH 2 CH CH CH 2 C OH
7 6 5 4 3

1. Cis form
2. Not conjugated --- isolated double bond.
3. Even numbered fatty acids.
CLASSIFICATION OF FATTY ACIDS PRESENT
AS GLYCERIDES IN FOOD FATS
Common Systematic Formula Common source
Name Name

I. Saturated Fatty Acids

Butyric Butanoic CH3(CH2)2COOH butterfat
Caproic Hexanoic CH3(CH2)4COOH butterfat, coconut
and palm nut oils
Caprylic Octanoic CH3(CH2)6COOH coconut and palm
nut oils, butterfat
Capric Decanoic CH3(CH2)8COOH coconut and palm
nut oils, butterfat
Lauric Dodecanoic CH3(CH2)10COOH coconut and palm
nut oils, butterfat
Myristic Tetradecanoic CH3(CH2)12COOH coconut and Palm nut oil, most
animal and plant fats
Palmitic Hexadecanoic CH3(CH2)14COOH practically all animal and
plant fats
Stearic Octadecanoic CH3(CH2)16COOH animal fats and minor
component of plant fats
Arachidic Eicosanoic CH3(CH2)18COOH peanut oil
CHARACTERISTICS OF FATTY ACIDS

Fatty Acids M.P.(0C) mg/100 ml Soluble in H2O

C4 -8 -
C6 -4 970
C8 16 75
C10 31 6
C12 44 0.55
C14 54 0.18
C16 63 0.08
C18 70 0.04
Effects of Double Bonds on the Melting Points

F. A. M. P. (0C)
16:0 60
16:1 1
18:0 63
18:1 16
18:2 -5
18:3 -11
20:0 75
20:4 -50

M.P.

# Double bonds
 FAT AND OILS

Mostly Triglycerides:

O
O
H2 C O C R
H2 C OH HO C R O
O
HC OH + HC O C R + 3 H2O
HO C R O
H2 C OH O
HO C R H2 C O C R

Glycerol 3 Fatty Acids

 GLYCERIDES

H2 C OH O
H2 C O C (CH2 )16 CH3
HC OH O
HC OH O
H2 C O C (CH2 )16 CH3
H2 C O C (CH2 )16 CH3
Monoglyceride (a - monostearin) Diglyceride (a, a' - distearin)
O
H2 C O C (CH2 )16 CH3 ( C18 )
O
HC O C (CH2 )14 CH3 (C16 )
O
H2 C O C (CH2 )16 CH3 (C18 )

Triglyceride (b - palmityl distearin)

Oleic
Palmitic OPP
Palmitic
a - oleodipalmitin
1 - oleodipalmitin
Linoleic
Oleic
LOO
Oleic
a - Linoleyldiolein
1 - Linoleyldiolein
MELTING POINTS OF TRIGLYCERIDES

Triglyceride Melting Point (°C)

C6 -15

C12 15

C14 33

C16 45

C18 55

C18:1 (cis) -32

C18:1 (trans) 15
 WAXES
Fatty acids + Long chain alcohol
Important in fruits:
1. Natural protective layer in fruits, vegetables, etc.
2. Added in some cases for appearance and protection.
Beeswax (myricyl palmitate), Spermaceti (cetyl palmitate)

O O
C30 H61 O C C15 H31 C16 H33 O C C15 H31
 PHOSPHOLIPID
Lecithin (phosphatidyl choline)

O
H2 C O C R
O
R C O CH
O CH3
+
H2 C O P O CH2 CH 2 N CH 3
O_ CH3
Phosphatidic Acid Choline
 STEROLS

Male & female sex hormones

Bile acids
Vitamin D
Adrenal corticosteroids
Cholesterol
21
22
H3C CH3
18
H3C 20
12
CH3
19 17 16
H3C 11 13 14
10 15
1 9
2 8
3 6 7
4
HO 5
 FAT SOLUBLE VITAMINS
Vitamin A:

H3 C CH3 CH3 CH3

5
8 CH2 OH
9 7 3 1
6 4 2

CH3
 CH3
H3C CH3
H3C
CH3

Vitamin D2:
H
H
CH2

HO

Vitamin E:

R1 CH3
O CH 3
R2 (CH2 CH2 CH2 CH2 )2 CH2 CH2CH2 CH(CH3 )2
HO
R3
ANALYTICAL METHODS TO MEASURE THE
CONSTANTS OF FATS AND OILS

1. Acid Value
2. Saponification Value
3. Iodine Value
4. Gas Chromatographic Analysis for Fatty Acids
5. Liquid Chromatography
6. Cholesterol Determination
 1. Acid Value

Number of mgs of KOH required to neutralize the Free

Fatty Acids in 1 g of fat.

ml of KOH x N x 56
AV = = mg of KOH
Weight of Sample
 2. Saponification Value

Saponification - hydrolysis of ester under alkaline

condition.

O
H2 C OH
H2 C O C R O
O +
+ 3 KOH HC OH 3 R C OK
HC O C R
O
H2 C OH
H2 C O C R
 2. Saponification Value Determination

Saponification # --mgs of KOH required to saponify 1 g of fat.

1. 5 g in 250 ml Erlenmeyer.
2. 50 ml KOH in Erlenmeyer.
3. Boil for saponification.
4. Titrate with HCl using phenolphthalein.
5. Conduct blank determination.

56.1(B - S) x N of HCl
SP# =
Gram of Sample

B - ml of HCl required by Blank.

S - ml of HCl required by Sample.
 3. Iodine Number

Number of iodine (g) absorbed by 100 g of oil.

Molecular weight and iodine number can calculate the

number of double bonds. 1 g of fat adsorbed 1.5 g of
iodine value = 150.
 Iodine Value Determination

Iodine Value = (ml of Na2S2O3 volume for blank - ml of Na2S2O3

volume for sample)  N of Na2S2O3  0.127g/meq  100
Weight of Sample (g)

CH CH + ICl CH CH
Iodine chloride Cl I

Excess unreacted ICl

ICl + KI KCl + I2

I2 + 2 Na2 S2 O3 Na2 S4 O6 + 2 NaI

 Iodine Numbers of Triglycerides

Fatty Acids # of Double-bonds Iodine #

Palmitoleic Acid 1 95

Oleic Acid 1 86

Linoleic Acid 2 173

Linolenic Acid 3 261

Arachidonic Acid 4 320

 4. GC Analysis for Fatty Acids

1. Extract fat.
2. Saponify (hydrolysis under basic condition).
3. Prepare methyl ester (CH3ONa).
4. Chromatography methyl ester.
5. Determine peak areas of fatty acids.
Fatty acids are identified by retention time.
6. Compare with response curve of standard.
 Fatty Acids Methyl Esters:

Response

18:1

14

18:3 21:1 24
16 18:2 20
18 22

Time

GC condition: 10% DEGS Column (from supelco)

Column temperature 200C.
 5. TRIGLYCERIDE ANALYSIS BY LIQUID
CHROMATOGRAPHY

Soybean Oil
Solvent CH3CN/HF
Column 84346 (Waters Associates)

RESPONSE

RETENTION TIME
 LIPID CONTENT ANALYSES

1. Gravimetric Method
(1) Wet extraction - Roese Gottliegb & Mojonnier.
(2) Dry extraction - Soxhlet Method.

2. Volumetric Methods (Babcock, Gerber Methods)

 1. Gravimetric Method

(1) Wet Extraction - Roese Gottlieb & Mojonnier.

For Milk:
1) 10 g milk + 1.25 ml NH4OH mix. solubilizes
protein and neutralizes.
2) + 10 ml EtOH - shake. Begins extraction, prevents
gelation of proteins.
3) + 25 ml Et2O - shake and mix.
4) + 25 ml petroleum ether, mix and shake.
 (2) Dry Extraction - Soxhlet Method.

Sample in thimble is continuously extracted with ether

using Soxhlet condenser. After extraction, direct
measurement of fat
- evaporate ether and weigh the flask.

Indirect measurement - dry thimble and weigh thimble and

sample.
Soxhlet Method.
 ANALYSIS OF FLAVOR QUALITY & STABILITY OF OIL

1. Peroxide Value

O O
A. KI + CH 3 C OH HI + CH 3 C OK

B. ROOH + 2 HI I2 + H2O + ROH

C. I2 + 2 Na2 S 2 O3 2 NaI + Na2 S4 O6

Peroxide Value = ml of Na2S2O3  N  1000

(milliequivalent peroxide/kg of sample) Grams of Oil
3. TBA Test.
To determine the rancidity degree of meat or fish product.

HS N OH O O
+ C CH2 C
N H H
OH

HS N OH HO N SH
+ 2 H2 O
N N
CH CH CH
OH OH
Colored Pigment