The Thermodynamic and Kinetic Basis of Liquid Chromatography

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The Thermodynamic and
Kinetic Basis of Liquid
Chromatography
Xiaoping Li, Amber M. Hupp,
and Victoria L. McGuffin
CONTENTS
I. Introduction....................................................................................................2
II. Theory............................................................................................................2
A. Thermodynamics ...................................................................................4
B. Kinetics..................................................................................................8
III. Methods........................................................................................................10
A. Perturbation Methods ..........................................................................10
1. Temperature Jump Method ...........................................................11
2. Pressure Jump Method..................................................................11
3. Dipole Jump Method.....................................................................12
B. Shallow Bed Method...........................................................................12
C. Chromatographic Methods..................................................................13
1. Frontal Method..............................................................................13
2. Impulse Method.............................................................................13
IV. Applications of Thermodynamic and Kinetic Methods..............................19
A. Partition ...............................................................................................19
1. Fundamental Studies of the Retention Mechanism......................20
2. Effect of Alkyl Chain Length and Bonding Density....................22
3. Effect of Support ...........................................................................33
4. Effect of Mobile Phase Composition............................................34
5. Effect of Solute Structure and Concentration...............................37
B. Adsorption ...........................................................................................45
1. Poly(styrene-divinylbenzene) ........................................................45
2. Porous Graphitic Carbon...............................................................47
3. Other Organic Adsorbents.............................................................52
4. Silica ..............................................................................................53
C. Ion Exchange.......................................................................................57
D. Size Exclusion .....................................................................................60

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