Critical conditions of polymer adsorption and chromatography on non-porous substrates

Richard T. Cimino, Christopher J. Rasmussen, Yefim Brun, Alexander V. Neimark

Research output: Contribution to journalArticlepeer-review

7 Scopus citations


We present a novel thermodynamic theory and Monte Carlo simulation model for adsorption of macromolecules to solid surfaces that is applied for calculating the chain partition during separation on chromatographic columns packed with non-porous particles. We show that similarly to polymer separation on porous substrates, it is possible to attain three chromatographic modes: size exclusion chromatography at very weak or no adsorption, liquid adsorption chromatography when adsorption effects prevail, and liquid chromatography at critical conditions that occurs at the critical point of adsorption. The main attention is paid to the analysis of the critical conditions, at which the retention is chain length independent. The theoretical results are verified with specially designed experiments on isocratic separation of linear polystyrenes on a column packed with non-porous particles at various solvent compositions. Without invoking any adjustable parameters related to the column and particle geometry, we describe quantitatively the observed transition between the size exclusion and adsorption separation regimes upon the variation of solvent composition, with the intermediate mode occurring at a well-defined critical point of adsorption. A relationship is established between the experimental solvent composition and the effective adsorption potential used in model simulations.

Original languageEnglish (US)
Pages (from-to)25-33
Number of pages9
JournalJournal of Colloid And Interface Science
StatePublished - Jul 15 2016

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Biomaterials
  • Surfaces, Coatings and Films
  • Colloid and Surface Chemistry


  • Adsorption
  • Critical conditions
  • Monte Carlo simulation
  • Polymer chromatography


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