JoVE Logo

Sign In

The rate theory of chromatography provides quantitative insight into the shapes and widths of elution bands. These bands are based on the random-walk mechanism governing molecular migration within a column. The Gaussian profile of chromatographic bands arises from the cumulative effect of random molecular motions as they progress through the column.

During elution, a solute molecule experiences numerous transitions between stationary and mobile phases, exhibiting irregular residence times in each phase. As a solute zone travels down the column, its width increases due to the increased dispersion time. This zone width is directly proportional to the column residence time and inversely proportional to the mobile-phase flow velocity.

The van Deemter equation elucidates the influence of the mobile phase's flow rate on the height of a theoretical plate. This equation comprises three factors: A, B, and C. Factor A represents the multiple paths available to a solute traversing a packed column (eddy diffusion). Factor B accounts for the longitudinal (axial) or molecular diffusion arising from solute dispersion between high-concentration central regions and low-concentration peripheral regions, and factor C pertains to the mass transfer of solutes within stationary and mobile phases.

Overall, a high mobile phase velocity increases the plate height, resulting in band broadening.

From Chapter 11:

article

Now Playing

11.7 : Column Efficiency: Rate Theory

Principles of Chromatography

108 Views

article

11.1 : Chromatographic Methods: Terminology

Principles of Chromatography

360 Views

article

11.2 : Chromatographic Methods: Classification

Principles of Chromatography

432 Views

article

11.3 : Analyte Adsorption and Distribution

Principles of Chromatography

291 Views

article

11.4 : Diffusion on Chromatography Columns

Principles of Chromatography

168 Views

article

11.5 : Chromatographic Resolution

Principles of Chromatography

137 Views

article

11.6 : Column Efficiency: Plate Theory

Principles of Chromatography

167 Views

article

11.8 : Optimizing Chromatographic Separations

Principles of Chromatography

190 Views

article

11.9 : Silica Gel Column Chromatography: Overview

Principles of Chromatography

554 Views

article

11.10 : Thin-Layer Chromatography (TLC): Overview

Principles of Chromatography

593 Views

article

11.11 : Gas Chromatography: Introduction

Principles of Chromatography

262 Views

article

11.12 : Gas Chromatography: Types of Columns and Stationary Phases

Principles of Chromatography

184 Views

article

11.13 : Gas Chromatography: Sample Injection Systems

Principles of Chromatography

165 Views

article

11.14 : Gas Chromatography: Overview of Detectors

Principles of Chromatography

163 Views

article

11.15 : Gas Chromatography: Types of Detectors-I

Principles of Chromatography

158 Views

See More

JoVE Logo

Privacy

Terms of Use

Policies

Research

Education

ABOUT JoVE

Copyright © 2025 MyJoVE Corporation. All rights reserved