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Experiment 24:



SYNTHESIS AND GC ANALYSIS OF

FATTY ACID METHYL ESTERS

O



CH2O C R





O CH2OH RCO2CH3

KOH

CHO C R' CHOH + R'CO2CH3

CH3OH

CH2OH R"CO 2CH3

O

Glycerol Fatty acid methyl esters

CH2O C R" forms CH3O-K+ (FAMES)

and H2O

Vegetable oil

Objectives:

 To synthesize fatty acid methyl esters

through transesterification of an unknown

vegetable oil.



 To purify your product using column

chromatography.



 To identify and analyze the purity of your

compound using TLC and GC analysis.



 To identify the unknown oil based on fatty

acid methyl ester composition.

CHEMICAL EQUATION

(Hydrolysis of a fat)









O



CH2O C R

O O



CH2OH R C O R C OH

O

-

OH O O

CHO C R' CHOH + H3O

R' C O R' C OH

CH2OH O O

O

Glycerol

R" C O R" C OH

CH2O C R"

Fatty Acid salts Fatty Acids

fat

CHEMICAL EQUATION

(Transesterification of vegetable oil)







O



CH2O C R

O



CH2OH R C O CH3

O

O

KOH

CHO C R' CHOH +

CH3OH R' C O CH3

CH2OH O

O

Glycerol

forms CH3O-K+ R" C O CH3

CH2O C R"

and H2O Fatty acid methyl esters

Vegetable oil (FAMES)

COMMON FATTY ACIDS

Saturated=

NO double bonds!

O

14 Myristic Acid (saturated) 16 O Palmitic Acid (saturated)

OH 14:0 16:0

OH



18 O Stearic Acid (saturated)

18:0

OH









18







18









OH Oleic Acid (monounsaturated)

9 18:1 9 12

O

OH Linoleic Acid (polyunsaturated)

9 18:2 9,12

Monounsaturated= O



ONE double bond! Polyunsaturated=

>one double bond!

SHAPES OF FATTY ACIDS



More cis double bonds = more “bent” shape

EXPERIMENTAL PROCEDURE

(Synthesis)





 Add 10 drops of unknown

oil and methanol to vial

with stir bar.

 Add 1M KOH/methanol.

 Stir in heat block.

 Attach reflux condenser.

 Heat to reflux. Maintain

temperature b/n 70-80oC

for 30 minutes.

 Cool flask.

EXPERIMENTAL PROCEDURE

(Purification and Isolation)





 DO NOT add Saturated NaCl

to vial.

MODIFICATION









 Extract product

 2X with hexane



 1X with 9:1 hexane: diethyl

ether.

 After each extraction step,

pass organic layer through SiO2

column into a small test tube.

 Proceed to PRODUCT

ANALYSIS.

EXPERIMENTAL PROCEDURE

(Product Analysis)





 TLC Analysis

 Perform analysis of product along with provided

standards of the unknown oil and FAMEs solutions.

 Must use 10% H2SO4 stain with heat in order to

visualize spots.

 Have stained TLC plate inspected by lab instructor.





 GC Analysis

 With instructor permission, prepare sample for GC

analysis.

GC ANALYSIS OF FAMES

STANDARD SOLUTION









• Oncereturned, identify and quantify FAMEs

present in your unknown oil.

• Compare these results to table on p. 201 in

order to identify your unknown oil.

Table 24.1





Be sure to give

CENTIMETER

measurements for

ALL spots and give

measurement for

SOLVENT FRONT

on this diagram!

Table 24.2

GC Retention Times (min) Area Adjusted

Compound Percent Area %

Standard Sample

XXX

pentane





Methyl Palmitate





Methyl Oleate





Methyl Linolate





Methyl Stearate

RELATIVE COMPOSITION OF OILS



Saturated Monounsaturated Polyunsaturated

Fatty Acids Fatty Acids Fatty Acids

Total % SFUs Total %

Name of Oil PUFAs

Myristic Palmitic Stearic Oleic Linoleic

C14 C16 C18 C18 C18

(14:0) (16:0) (18:0) (18:19) (18:19,12)





Corn 0 11 2 13 28 58 59



Olive 0 13 3 16 71 10 11



Peanut 0 11 2 13 48 32 32



Soybean 0 11 4 15 24 54 61



Safflower 0 7 2 9 13 78 78



Cottonseed 1 22 3 26 19 54 55



Palm 1 45 4 50 40 10 10

Table 24.3

Did you use UNKNOWN A, B, or C?

Unknown Letter



 Once you have a tentative identification

% SFA of your unknown vegetable oil based on

your comparison of the calculated values

in Table 24.2 to the table on p. 201 of

%MUFA your lab manual, complete this table by

filling in the EXPECTED % for your oil

using the values provided in the table on p.

201.

%PUFA

These values may not match your

calculated values EXACTLY, but should be

close enough for you to have verification

of the identity of your unknown oil!

Give the name of your unknown oil here!

Unknown Identity

SAFETY CONCERNS



CAUTION:

SULFURIC ACID and POTASSIUM

HYDROXIDE are very corrosive!



 HEXANE and DIETHYL ETHER are

extremely flammable!



 METHANOL is very flammable and toxic!

WASTE MANAGEMENT

• All liquid waste in container labeled “ORGANIC

WASTE (FAMEs).



• Leave TLC plates with instructor.



• Place filter papers in the yellow SOLID WASTE

can.



• Place used TLC capillaries, SiO2 columns, and

glass Pasteur pipets in broken glass container.

CLEANING



 Rinse all glassware with wash acetone

ONLY!

 DO NOT return any glassware to lab

drawer dirty or wet!



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