Micellar liquid chromatography

Lecture-7
 Micellar Liquid Chromatography

Armstrong, Cline-love and

Foley’s equation

1 1 KAM
   M
k KAS KAS
KAS
KAM

Introduced by Armstrong (Washington)

What are Amphiphilic Surfactants

O
O
O
+
Na-O S
O O
O
Aerosol OT

Amphiphilic surfactants contain a non-polar portion and

a polar portion.
 Classification of Surfactants
O
• Anionic S - +
O Na
O
• Cationic Sodium dodecylsulfate (SDS)
• Zwitterionic +
• Nonionic N
Br-
Cetylpyridinium bromide
O
O
O OCH2CH2N(CH3)3+
P O-
O
O
Dipalmitoylphosphatidylcholine (lecithin)

O O OH
O O
Polyoxyethylene(4) lauryl ether (Brij 30)
 Solubility Effects

• Solubility of a poorly soluble compound increases

as a result of solubilization in the micelles

14
Solubility

12
10
8
6
CMC
4
2
0
0 1
Surfactant concentration
 Advantages of MLC
• Determination of Micelle binding constant is possible for the
compounds experiencing variable retention times by varying
surfactant concentration.

• Micellar binding constants have specific applications in micellar

catalysis, Tertiary oil recovery and enzyme and membrane
modeling.

• Simultaneous separation of mixture of ionic and non-ionic

compounds.
• Micellar eluents are non-toxic and inexpensive.

• Selectivity parameters depend on nature and charge of

surfactant, concentration of additive, ionic strength and
pH.

• Micellar gradients expedite separations.

• Biological activity of many sorbates is predictable.

Chromatogram of Metal-pyridylazoresorcinol
complxes

Separation of Co, Fe(II), Fe(III) and Ni

using 0.1M CTAB and 20% acetonitrile
Co (1), Fe-II (2), Fe-III (3) and Ni (4)
with retention times 9.5, 15.1, 15.4 and
18.2 respectively.
SEPARATION of preservatives USING Brij-35
70
Voltage ( mV)

-1.0
0 Minutes 20
 1
4
100

Chromatographic conditions
• 0.1 M CTAB at pH 2.5
• 0.7 ml/min
• Cyano 25 cm
Voltage (mV)

• 280 nm
3
2
1. Pyridoxine
2. Nicotinmaide
3. B2
0 4. Ascorbic acid
0 Minutes 7
 20

Vitamin E-
alcohol Vitamin
A-acetate

Vitamin
Voltage (mV)

E-acetate
• Chromatographic Conditions
• 0.1 M CTAB+10%Propanol+10%THF
• 0.4 ml/min
• Cyano 25 cm
• 280 nm

-5
0 15
Minutes
 Publication from this work
• “Study on the Character of Interactions between Metal-Pyridylazo
Resorcinol Complexes and Cationic Surfactants by Spectrophotometry
and Chromatography”, Najma Memon, Analytical Chemistry: An
Indian Journal, Vol.3 (4-6) 2007.

• Determination of Preservatives in Cosmetics and Food Samples by

Micellar Liquid Chromatography” Najma Memon, M. Iqbal Bhanger,
M.Y. Khuhawer, Journal of Separation Science, 28 (2005) 635-638.

• “Micellar liquid chromatographic determination of aluminum using 8-

hydroxyquinoline-5-sulphonic acid”, N. Memon, M.I. Bhanger, Acta
Chromatographica, 14(2004) 172-179.