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:
Now Playing
Principles of Chromatography
108 Views
Principles of Chromatography
360 Views
Principles of Chromatography
432 Views
Principles of Chromatography
291 Views
Principles of Chromatography
168 Views
Principles of Chromatography
137 Views
Principles of Chromatography
167 Views
Principles of Chromatography
190 Views
Principles of Chromatography
554 Views
Principles of Chromatography
593 Views
Principles of Chromatography
262 Views
Principles of Chromatography
184 Views
Principles of Chromatography
165 Views
Principles of Chromatography
163 Views
Principles of Chromatography
158 Views
See More
Copyright © 2025 MyJoVE Corporation. All rights reserved