A phenomenological one-parameter equation of state for osmotic pressures of PEG and other neutral flexible polymers in good solvents

J Phys Chem B. 2009 Mar 26;113(12):3709-14. doi: 10.1021/jp806893a.

Abstract

We present a phenomenological one-parameter scaling equation of state that accurately represents osmotic pressures of neutral flexible polymers in good solvents from the dilute through the semidilute regime. The equation comprises a sum of scaled van't Hoff and des Cloizeaux terms including a fitted parameter alpha, the "crossover index", which encapsulates all chemical specificity and determines the relevant prefactors. Strikingly different values of alpha are found for the two very different systems poly(ethyleneglycol)/water (PEG) and poly(alpha-methylstyrene)/toluene (PAMS). Alpha-dependent rescaling collapses both data sets to a simple one-parameter scaling function. The fact that the anomalous system PEG/water and the canonical system PAMS/toluene can both be described by the same equation of state attests to the robustness of the polymer-scaling concepts introduced by de Gennes.

Publication types

  • Research Support, N.I.H., Intramural

MeSH terms

  • Osmotic Pressure
  • Polyethylene Glycols / chemistry*
  • Solvents / chemistry
  • Styrenes / chemistry*
  • Toluene / chemistry*
  • Water / chemistry*

Substances

  • Solvents
  • Styrenes
  • Water
  • vinyltoluene
  • Toluene
  • Polyethylene Glycols