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

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

The journal of physical chemistry. B (2009-03-07)
J A Cohen, R Podgornik, P L Hansen, V A Parsegian
RÉSUMÉ

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.

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Methylstyrene, 60% meta, 40% para and 1% ortho, 99%, contains ~50 ppm 4-tert-butylcatechol as inhibitor