Correspondence between chromatography, single-molecule dynamics, and equilibrium: a stochastic approach

Area of Science:

• Analytical Chemistry
• Physical Chemistry
• Surface Science

Background:

• Chromatography, single-molecule measurements, and phase equilibrium are key experimental techniques.
• Understanding the interplay between these methods is crucial for advanced separation science.
• Stochastic descriptions offer a unifying framework for analyzing dynamic processes.

Purpose of the Study:

• To establish a fundamental correspondence between chromatographic separations, single-molecule interface dynamics, and phase partition equilibrium.
• To derive expressions for errors in the retention factor linked to various separation phenomena.
• To explore the impact of single-molecule dynamics on chromatographic peak shape and species behavior at interfaces.

Main Methods:

• Utilizing a unifying stochastic description approach.
• Deriving expressions for retention factor errors from basic principles.
• Applying the framework to microsystems, nanosystems, and chip technology with numerical examples.

Main Results:

• Established full correspondence between the three experimental techniques.
• Derived general expressions for errors on the retention factor, including peak splitting, tailing, and molecular number effects.
• Quantified the impact of single-molecule dynamics on chromatographic peak shape and sorption time distribution.

Conclusions:

• The stochastic approach provides a robust framework for linking diverse experimental techniques in separation science.
• Accurate error analysis in chromatography is essential and can be improved by considering single-molecule dynamics.
• This work has implications for advanced analytical techniques in micro/nanosystems and chip technology.