Concentration dependence of the Flory-Huggins interaction parameter in aqueous solutions of capped PEO chains

M. I. Chaudhari; L. R. Pratt; M. E. Paulaitis

doi:10.1063/1.4904386

Concentration dependence of the Flory-Huggins interaction parameter in aqueous solutions of capped PEO chains

M. I. Chaudhari, L. R. Pratt, M. E. Paulaitis

School of Medicine

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Abstract

The dependence on volume fraction φ of the Flory-Huggins interaction parameter χ wp φ describing the free energy of mixing of polymers in water is obtained by exploiting the connection of χ wp φ to the chemical potential of the water, for which quasi-chemical theory is satisfactory. We test this theoretical approach with simulation data for aqueous solutions of capped PEO (polyethylene oxide) oligomers. For CH₃(CH₂-O-CH₂)_mCH₃ (m = 11), χ wp φ depends strongly on φ, consistent with experiment. These results identify coexisting water-rich and water-poor solutions at T = 300 K and p = 1 atm. Direct observation of the coexistence of these two solutions on simulation time scales supports that prediction for the system studied. This approach directly provides the osmotic pressures. The osmotic second virial coefficient for these chains is positive, reflecting repulsive interactions between the chains in the water, a good solvent for these chains.

Original language	English (US)
Article number	244908
Journal	Journal of Chemical Physics
Volume	141
Issue number	24
DOIs	https://doi.org/10.1063/1.4904386
State	Published - Dec 28 2014

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "Concentration dependence of the Flory-Huggins interaction parameter in aqueous solutions of capped PEO chains",

abstract = "The dependence on volume fraction φ of the Flory-Huggins interaction parameter χ wp φ describing the free energy of mixing of polymers in water is obtained by exploiting the connection of χ wp φ to the chemical potential of the water, for which quasi-chemical theory is satisfactory. We test this theoretical approach with simulation data for aqueous solutions of capped PEO (polyethylene oxide) oligomers. For CH3(CH2-O-CH2)mCH3 (m = 11), χ wp φ depends strongly on φ, consistent with experiment. These results identify coexisting water-rich and water-poor solutions at T = 300 K and p = 1 atm. Direct observation of the coexistence of these two solutions on simulation time scales supports that prediction for the system studied. This approach directly provides the osmotic pressures. The osmotic second virial coefficient for these chains is positive, reflecting repulsive interactions between the chains in the water, a good solvent for these chains.",

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AU - Chaudhari, M. I.

AU - Pratt, L. R.

AU - Paulaitis, M. E.

PY - 2014/12/28

Y1 - 2014/12/28

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AB - The dependence on volume fraction φ of the Flory-Huggins interaction parameter χ wp φ describing the free energy of mixing of polymers in water is obtained by exploiting the connection of χ wp φ to the chemical potential of the water, for which quasi-chemical theory is satisfactory. We test this theoretical approach with simulation data for aqueous solutions of capped PEO (polyethylene oxide) oligomers. For CH3(CH2-O-CH2)mCH3 (m = 11), χ wp φ depends strongly on φ, consistent with experiment. These results identify coexisting water-rich and water-poor solutions at T = 300 K and p = 1 atm. Direct observation of the coexistence of these two solutions on simulation time scales supports that prediction for the system studied. This approach directly provides the osmotic pressures. The osmotic second virial coefficient for these chains is positive, reflecting repulsive interactions between the chains in the water, a good solvent for these chains.

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Concentration dependence of the Flory-Huggins interaction parameter in aqueous solutions of capped PEO chains

Abstract

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