Lipids

Types of Lipids
Fatty Acids
Fats, and Oils
Chemical Properties of Triglycerides
1
Compiled by: Dwika Riandari, M.Si
Teaching material for Proximate Analysis
Introduction
Definition: water insoluble compounds
Most lipids are fatty acids or ester of fatty acid
They are soluble in non-polar solvents such as
petroleum ether, benzene, chloroform
Functions
Energy storage
Structure of cell membranes
Thermal blanket and cushion
Precursors of hormones (steroids and
prostaglandins)



2
Types of Lipids
Lipids with fatty acids
Waxes
Fats and oils (trigycerides)
Phospholipids
Sphingolipids

Lipids without fatty acids
Sterol
3
4
Waxes
Fatty acid + 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
C
30
H
61
O C C
15
H
31

O
C
16
H
33
O C C
15
H
31
5
Bees wax
Spermaceti source
Carnauba wax source
TRIACONTANOILPALMITAT

LILIN PADA LEBAH MADU
(BEE)
7
Phospholipid
Lecithin (phosphatidyl choline)

O
O
H
2
C O C R
O
R C O CH
H
2
C O P O CH
2
CH
2
N
+
CH
3
CH
3
CH
3
O_
Phosphatidic Acid
Choline
Two hydroxyls of the glycerol residue are esterfied with fatty acids
The third hydroxyl is bound to phosphoric acid which in turn is
ester-linked with X-OH, usually an amine alcohol
8
The phosphoric acid end of the molecule is strongly polar
hydrophylic
The fatty acid tails are non-polar
This dual structure (amphiphathic) makes the phosphoglycerides
valuable surface active agents and emulsion stabilizers
Phosphoglycerides are important cell wall constituent
9
Sterols
Male & female sex hormones
Bile acids
Vitamin D
Adrenal corticosteroids
Cholesterol

HO
H
3
C
H
3
C
H
3
C CH
3
CH
3
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16 17
18
21
22
19
20
HO
STEROID NUMBERING SYSTEM
A B
C
D
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
11
Fat Soluble Vitamins
Vitamin A

CH
2
OH
CH
3
CH
3
CH
3
CH
3
H
3
C
1
2
3
4
5
6
7
8
9
12
Vitamin D2
Vitamin E

HO
CH
2
H
H
H
3
C
H
3
C CH
3
CH
3
CH
3

O
R
1
R
2
HO
R
3
CH
3
(CH
2
CH
2
CH
2
CH
2
)
2
CH
2
CH
2
CH
2
CH(CH
3
)
2
CH
3
Fatty Acids
Long-chain carboxylic acids
Insoluble in water
Typically 12-18 carbon atoms (even number)
Some contain double bonds

corn oil contains 86%
unsaturated fatty acids and
14% saturated fatty acids
13
Saturated and Unsaturated Fatty Acids
Saturated = CC bonds
Unsaturated = one or more C=C bonds
14
Palmitic acid, a saturated acid
Palmitoleic acid, a unsaturated fatty acid
COOH
COOH
Structures
Saturated fatty acids
Fit closely in regular pattern


Unsaturated fatty acids
Cis double bonds



15
COOH
COOH
COOH
C C
H
H
C O O H c i s d o u b l e b o n d


Properties of Saturated
Fatty Acids
Contain only single CC bonds
Closely packed
Strong attractions between chains
High melting points
Solids at room temperature
16
17
Saturated Fatty Acids


Butyric

Butanoic

CH3(CH2)2COOH

butterfat

Caproic

Hexanoic

CH3(CH2)4COOH

butterfat, coconut, palm nut oils

Caprylic

Octanoic

CH3(CH2)6COOH

Coconut, palm, nut oils, butterfat

Capric

Decanoic

CH3(CH2)8COOH

Coconut, palm, nut oils, butterfat

Lauric

Dodecanoic

CH3(CH2)10COOH

Coconut, palm, nut oils, butterfat

Myristic

Tetradecanoic

CH3(CH2)12COOH

Coconut, palm, nut oil, animal fats

Palmitic

Hexadecanoic

CH3(CH2)14COOH

practically all animal, plant fats

Stearic

Octadecanoic

CH3(CH2)16COOH

animal fat, plant fats

Arachidic

Eicosanoic

CH3(CH2)18COOH

peanut oil

Common
Name

Systematic
Name

Formula

Common source

Properties of Unsaturated
Fatty Acids
Contain one or more double C=C bonds
Nonlinear chains do not allow molecules to pack
closely
Few interactions between chains
Low melting points
Liquids at room temperature
18
Unsaturated Fatty Acids
19


Common
Name

Systematic
Name

Formula

Common source



A. Monoethenoic Acids


Oleic

Cis 9-octadecenoic

C17H33COOH

plant and animal fats

Elaidic

Trans 9-Octadecenoic

C17H33COOH

animal fats

B. Diethenoic Acids

Linoleic

9,12-Octadecadienoic

C17H31COOH

peanut, linseed, and
cottonseed oils

C. Triethenoid Acids


Linolenic

9,12,15-Octadecatrienoic

C17H29COOH

linseed and other seed
oils

Eleostearic

9,11,13-Octadecatrienoic

C17H29COOH

peanut seed fats

D. Tetraethenoid Acids

Moroctic

4,8,12,15-
Octadecatetraenoic

C17H27COOH

fish oils

Arachidonic

5,8,11,14-
Eicosatetraenoic

C19H31COOH

traces in animal fats

20
C4

- 8

-

C6

- 4

970

C8

16

75

C10

31

6

C12

44

0.55

C14

54

0.18

C16

63

0.08

Fatty Acids

M.P.(C)

mg/100 ml in H2O*

C18

70

0.04

Characteristics of Fatty Acids
* Solubility
Effects of Double Bonds on the Melting Points
Fatty Acids Melting point (C)
16:0 60
16:1 1
18:0 63
18:1 16
18:2 -5
18:3 -11
20:0 75
20:4 -50
21
M.P.
# Double bonds
x
x
x
x
Important Fatty Acids for Nutrition
EPA (Eicosapentaenoic acid)
20:5(n-3). Omega-3, all-cis eicosa-5,8,11,14,17
pentaenoic acid

DHA (Docosahexaenoic acid)
22:6 (n-3). omega-3, all-cis -docosa-4,7,10,13,16,19-
hexaenoic acid
22
Typical fish oil supplements
23
Fats and Oils
Formed from glycerol and fatty acids

24
+
H O C ( C H
2
)
1 4
C H
3
O
H O C ( C H
2
)
1 4
C H
3
O
H O C ( C H
2
)
1 4
C H
3
O
g l y c e r o l
p a l m i t i c a c i d ( a f a t t y a c i d )

C H
C H
2
O H
O H
C H
2
O H
Triglycerides (triacylglcerols)
Esters of glycerol and fatty acids
25
C H
C H
2
C H
2
O
O
O
C ( C H
2
)
1 4
C H
3
O
C ( C H
2
)
1 4
C H
3
O
C ( C H
2
)
1 4
C H
3
O
e s t e r b o n d s
+
+
+
H
2
O
H
2
O
H
2
O

Properties of fats and oils
fats are solids or semi solids
oils are liquids
melting points and boiling points are not usually
sharp (most fats/oils are mixtures)
when shaken with water, oils tend to emulsify
pure fats and oils are colorless and odorless (color
and odor is always a result of contaminants) i.e.
butter (bacteria give flavor, carotene gives color)
26
Examples of oils
Olive oil from Oleo europa (olive tree)
Corn oil from Zea mays
Peanut oil from Arachis hypogaea
Cottonseed oil from Gossypium
Sesame oil from Sesamum indicum
Linseed oil from Linum usitatissimum
Sunflower seed oil from Helianthus annuus
Rapeseed oil from Brassica rapa
Coconut oil from Cocos nucifera

27
Non-drying, semi-drying and drying
oils
based on the ease of autoxidation and
polymerization of oils (important in paints and
varnishes)
the more unsaturation in the oil, the more likely
the drying process
Non-drying oils:
Castor, olive, peanut, rapeseed oils
Semi-drying oils
Corn, sesame, cottonseed oils
Drying oils
Soybean, sunflower, hemp, linseed, tung, oiticica oils
28
29
Fatty Acids (%) of Fats and Oils
4

3







6

3







8

2

6





10

3

6





12

3

44





14

10

18

1



16

26

11

4

12

16:1

7



1



18:0

15

6

3

2

18:1

29

7

18

24

18:2

2

2

53

54

Fatty Acids

Butter

Coconut

Cottonseed

Soybean

18:3

2





8

Properties of Triglycerides
Hydrogenation
Unsaturated compounds react with H
2

Ni or Pt catalyst
C=C bonds CC bonds

Hydrolysis
Split by water and acid or enzyme catalyst
Produce glycerol and 3 fatty acids



30
Hydrogenation


31

C H
C H
2
C H
2
O
O
O
C
O
( C H
2
)
5
C H C H ( C H
2
)
7
C H
3
C
O
( C H
2
)
5
C H C H ( C H
2
)
7
C H
3
C
O
+

( C H
2
)
5
C H C H ( C H
2
)
7
C H
3
H
2
3
N i


Product of Hydrogenation







Hydrogenation converts double bonds in oils to single
bonds. The solid products are used to make
margarine and other hydrogenated items.







32
C H
C H
2
C H
2
O
O
O
C ( C H
2
)
1 4
C H
3
O
C ( C H
2
)
1 4
C H
3
O
C ( C H
2
)
1 4
C H
3
O
Hydrolysis
Triglycerides split into glycerol and three fatty
acids (H
+
or enzyme catalyst)
33



C H
C H
2
C H
2
O
O
O
C ( C H
2
)
1 4
C H
3
O
C ( C H
2
)
1 4
C H
3
O
C ( C H
2
)
1 4
C H
3
O
H
2
O + 3
3
+ H O C ( C H
2
)
1 4
C H
3
O
C H
C H
2
O H
O H
C H
2
O H


H
+
Saponification and Soap
Hydrolysis with a strong base
Triglycerides split into glycerol and the salts of fatty
acids
The salts of fatty acids are soaps
KOH gives softer soaps
34
Soaps
Process of formation is known as saponification
Types of soaps:
Sodium soap ordinary hard soap
Potassium soap soft soap (shaving soaps are potassium
soaps of coconut and palm oils)
Castile soap sodium soap of olive oil
Green soap mixture of sodium and potassium linseed oil
Transparent soap contains sucrose
Floating soap contains air
Calcium and magnesium soaps are very poorly water soluble
(hard water contains calcium and magnesium salts these
insolubilize soaps)

35
Saponification

36

3
+ N a
+

-
O C ( C H
2
)
1
6
C H
3
O
C H
C H
2
O H
O H
C H
2
O H





C H
C H
2
C H
2
O
O
O
C ( C H
2
)
1 6
C H
3
O
C
O
( C H
2
)
1 6
C H
3


( C H
2
)
1 6
C H
3 C
O
+ 3 N a O H
s a l t s o f f a t t y a c i d s ( s o a p s )






Learning Check L1
How would the melting point of stearic
acid compare to the melting points of oleic
acid and linoleic acid? Assign the melting
points of 17C, 13C, and 69C to the
correct fatty acid. Explain.
stearic acid (18 C)
oleic acid (18 C)
linoleic acid (18 C)
37
Solution L1
Stearic acid is saturated and would have a higher
melting point than the unsaturated fatty acids.
Because linoleic has two double bonds, it would
have a lower mp than oleic acid, which has one
double bond.
stearic acid mp 69C
oleic acid mp 13C
38
linoleic acid mp -17C
Learning Check L2
What are the fatty acids in the following
triglyceride?

39



C H
C H
2
C H
2
O
O
O
C ( C H
2
)
1 6
C H
3
O
C
O
( C H
2
)
7
C H C H ( C H
2
)
7
C H
3
C
O
( C H
2
)
1 2
C H
3


Solutions L2
What are the fatty acids in the following
triglyceride?


40
Stearic acid
Oleic acid
Myristic acid



C H
C H
2
C H
2
O
O
O
C ( C H
2
)
1 6
C H
3
O
C
O
( C H
2
)
7
C H C H ( C H
2
)
7
C H
3
C
O
( C H
2
)
1 2
C H
3


Learning Check L3
What are the products obtained from the complete
hydrogenation of glyceryl trioleate?

(1) Glycerol and 3 oleic acids
(2) Glyceryltristearate
(3) Glycerol and 3 stearic acids
41
Solution L3
What are the products obtained from the complete
hydrogenation of glyceryl trioleate?

2. Glyceryltristearate

42
Analytical Methods for The
Determination of Characteristics of
Fats and Oils

43
44
1. Acid Value
2. Saponification Value
3. Iodine Value
4. Gas Chromatographic Analysis for Fatty Acids
5. Liquid Chromatography
6. Cholesterol Determination
Analytical Methods
45
Acid Value
Number of mgs of KOH required to neutralize the Free
Fatty Acids in 1 g of fat.
AV =
ml of KOH x N x 56
Weight of Sample
= mg of KOH
RCOOH + KOH RCOO
-
K
+

+ H2O
Acid Value
46
The free fatty acid content in a good soybean oil should be
less than or equal to 0.05 %. The average molecular
weight of free fatty acids of the oil is 280 which is the
molecular weight of linoleic acid.
What is the maximum acid value of the good soybean oil?

What is the content (%) of free fatty acids of a soybean
oil if the acid value is 0.3? The average molecular weight
of free fatty acids of the oil is 280.
The free fatty acid content in soybean oil is
0.05%.
What is the content of free fatty acid in 1g oil in
mg?
1g = 1000mg
What is the 1% of 1000mg in mg?
What is the 0.1% of 1000 mg soybean oil in mg?
What are the 0.5% of 1000mg soybean oil in mg
and ug?
47
Acid Value
48

0.05 % in 1 gram is 0.5 mg RCOOH in 1 gram of oil
56 mg of KOH reacts with 280 mg of RCOOH
56 mg of KOH / 280 mg of RCOOH = 1 : 5
The 0.5 mg RCOOH reacts with 0.1 mg KOH
Acid Value is 0.1 mg KOH/g oil


What is the content (%) of free fatty acids of
soybean oil if the acid value is 0.3?
Acid value 0.3 means that 0.3 mg KOH is required
to react with the free fatty acid in1g (1000mg) of
oil
The 56mg KOH reacts with 280 mg free fatty acid,
56 : 280 =1 : 5
1mg KOH reacts with 5 mg free fatty acid
The 0.3 mg KOH reacts with 1.5 mg of free fatty
acid in 1 gram oil
1.5 mg free fatty acid /1000 mg oil x100(%) =0.15
%
49
50
Saponification Value
Saponification - Hydrolysis of ester (triglycerider)
under alkaline condition.

O
C R
O
O
C R
C R
O
H
2
C O
HC O
H
2
C O
KOH
H
H
H
H
2
C O
HC O
H
2
C O
R C O
-
K
+
+
3
+
3
Heat
Definition : mgs of KOH required to saponify 1 g of fat
51
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.

Saponification number =[ (B S) x N of HCl x 56] /gram of sample

B - ml of HCl required to titrate KOH in Blank.
S - ml of HCl required to titrate excess KOH by Sample.
Saponification Value Determination
Saponification Value
52

CH
2
O C
O
(CH
2
)
6
CH
3
CH O
C
O
(CH
2
)
6
CH
3
CH
2
O C
O
(CH
2
)
6
CH
3

CH
2
O C
O
(CH
2
)
16
CH
3
CH O C
O
(CH
2
)
16
CH
3
CH
2
O C
O
(CH
2
)
16
CH
3
Tricaprylin (MW= 450)
Tristearin (MW= 890)
1Gram of Oils A and B
A
B
Saponification Value
1 mol TG 3 mol KOH required

MW
KOH
= 56 g/mol, therefore weight of 1 mol KOH = 56000 mg
1 g TG => 1 g / MW
TG
(g/mol) mol


1 mol TG 3x 56000 mg KOH required
1 g TG / MW
TG
Xmg KOH required




53
TG
MW
168000
SN X
Saponification Value



What is the MW
TG
?

54
TG
MW
168000
SV X
O
C
C
O
C
O
O
O
O
- R

- R

- R

HC
H
2
C
H
2
C
O
C
C
O
C
O
O
O
O
- R1

- R1

- R2

HC
H
2
C
H
2
C
O
C
C
O
C
O
O
O
O
- R1

- R2

- R3

HC
H
2
C
H
2
C
Saponification Value



Which ones MW
should be taken?

TG
MW
168000
SV X
55
O
C
C
O
C
O
O
O
O
- R

- R

- R

HC
H
2
C
H
2
C
O
C
C
O
C
O
O
O
O
- R1

- R1

- R2

HC
H
2
C
H
2
C
O
C
C
O
C
O
O
O
O
- R1

- R2

- R3

HC
H
2
C
H
2
C
Saponification Value



The Answer is the Weighted Average MW

56
TG
AMW
168000
SV X
O
C
C
O
C
O
O
O
O
- R

- R

- R

HC
H
2
C
H
2
C
O
C
C
O
C
O
O
O
O
- R1

- R1

- R2

HC
H
2
C
H
2
C
O
C
C
O
C
O
O
O
O
- R1

- R2

- R3

HC
H
2
C
H
2
C
57
Sample A has large molecular weight triglyceride (e.g. MW.890).
Sample B has small molecular weight triglyceride(e.g. MW.450).
In one gram of sample, number of triglyceride in B is about two times
more than number of triglyceride in A.

Less mg of KOH is needed to saponify sample A than sample B.
Therefore, saponification value of A is about half of that of sample B

Avogadros Number (N) = 6.02 x 10
23
/ mol
Learning Check
58
A 5.00 grams of exotic tropical oil was saponified
with excess KOH. The unreacted KOH was then
titrated with 1.00 N HCl. The blank required 40 mL
of HCl and the sample required 20 mL.
Please calculate the saponification value of the oil.
Please calculate the MW
TG
How many base should be added to saponify 1000 g
of oil?

59
Milk Fat

210-233

Coconut Oil

250-264

Cotton Seed Oil

189-198

Soybean Oil

189-195


Fat


Saponification #

Lard

190-202


Saponification Values of Fats and Oils
60
Iodine Value
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
61
Trilinolein (MW= 878)
Triolein (MW= 884)
C H
2
O C
O
( C H
2
)
7
C H
C H ( C H
2
)
7
C H
3
C H
3
( C H
2
)
7
C H C H ( C H
2
)
7
O
C O C H
C H
3
( C H
2
)
7
C H C H ( C H
2
)
7
O
C O C H
2
CH
2
O C
O
(CH
2
)
7
CH CH CH
2
CH
CH CH (CH
2
)
7
O
C O CH
CH CH (CH
2
)
7
O
C O CH
2
CH (CH
2
)
4 CH
3
CH
3
(CH
2
)
4
CH CH CH
2
CH
3
(CH
2
)
4
CH CH CH
2
A
B
62
(ml of Na
2
S
2
O
3
volume for blank - ml of Na
2
S
2
O
3

volume for sample) N of Na
2
S
2
O
3
0.127g/meq 100
Weight of Sample (g)

ICl
KI
KCl
I
2
I
2
Na
2
S
2
O
3
Na
2
S
4
O
6
NaI
+
+
2
2
+
+
Excess unreacted ICl
Iodine Value Determination
Iodine Value =

CH CH
CH CH
Cl
I
ICl
Iodine chloride
+
_
_
Determination of Double Bonds per
Molecule
63
Iodine Value x Molecule Weight
2 x 127 x 100
Number of Double
Bonds per Molecule
=
Double Bond Determination
64
The unknown compound has molecular weight
of 878 and iodine value of 173. Determine the
number of double bonds in the unknown
compound

Fatty acids A and B have only one double bond per
molecule. The molecular weights of A and B are 150
and 300, respectively. The hypothetical iodine value
of Compound A is 150. What is the Iodine value of
compound B?

Triglycerides A and B have the very similar molecular
weights of about 878. The compound A has 6 double
bonds per molecule and has iodine value is 174. The
compound B has 3 double bond per molecule. What
is the iodine value of the compound B?

65
Learning Check
THE END
PS: GOOD LUCK ON YOUR TEST!
66