Transfer Thermodynamics

Beezer, Anthony E.; Milès, Roger; Perry, B. F.

doi:10.1016/b978-0-7236-0909-4.50012-7

Cited by 2 publications

(1 citation statement)

References 30 publications

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“…An earlier investigation of the thermodynamics of partitioning of a homologous series of alkoxyphenols between aqueous and organic phases provides data that support the same proposition. In that study, Beezer and co-workers estimated entropies of transfer for the methylene unit (CH 2 ) and a “parent structure”, in that case, HO(C 6 H 4 )O, between mutually saturated phases produced by mixing water with heptane, octanol, or propylene carbonate.…”

Section: Resultsmentioning

confidence: 71%

Entropically Driven Partitioning of Ethylene Oxide Oligomers and Polymers in Aqueous/Organic Biphasic Systems

2002

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Partitioning of ethylene oxide oligomers and polymers (PEO) in biphasic systems of water and chloroform or dichloromethane favors transfer to the organic phase as the molecular weight increases. For systems containing chlorobenzene, partitioning into the aqueous phase is always predominant. Calorimetric determination of the enthalpies of transfer for PEO from aqueous to organic phases reveals an endothermic process for all of the systems investigated, which was ascribed to the replacement of a more energetically favored PEO solvation in water for that in the organic phase. These results indicate that spontaneous PEO transfer from water to an organic phase is driven by an entropy increase. The number of water molecules transferred to the organic phase with PEO was determined to be ca. 0.08 water molecules per EO unit, smaller than hydration numbers reported in aqueous solutions. All of these findings lead to a picture where PEO may be extracted from water to an organic phase as long as the solvation by the organic solvent is relatively strong as compared to water. The displacement of water causes an entropy increase, which drives the transfer process. Chloroform and dichloromethane are suitable solvents for PEO extraction probably because of their hydrogen bonddonating capability.

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Section: Resultsmentioning

confidence: 71%

Entropically Driven Partitioning of Ethylene Oxide Oligomers and Polymers in Aqueous/Organic Biphasic Systems

2002

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Thermodynamics of the partitioning of poly(propylene oxide) between aqueous and chlorinated organic phases compared to poly(ethylene oxide) and other hydrophilic polymers

Anselmo¹,

Sassonia²,

Loh³

2006

J of Physical Organic Chem

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Thermodynamic functions associated with the partitioning of poly(propylene oxide), PPO, between aqueous and organic (chloroform, dichloromethane, and chlorobenzene) phases were determined and analyzed in comparison with those for the partitioning of poly(ethylene oxide), PEO, and poly(vinyl pyrrolidone), PVP. Amounts of water accompanying the partitioning of PPO to the organic phases were also measured. These results reveal that PPO partitioning is controlled by hydrophobic effects (entropic contribution), which was confirmed by the release of a significant amount of water molecules following the partitioning. Hydrophilic polymers like PVP and polyacrylamide, on the other hand, remain almost quantitatively in the aqueous phase. PEO remains a unique example of a polymer displaying high affinity for water, but that can be extracted to certain organic solvents (which should display hydrogen bond donating capacity).

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Transfer Thermodynamics

Cited by 2 publications

References 30 publications

Entropically Driven Partitioning of Ethylene Oxide Oligomers and Polymers in Aqueous/Organic Biphasic Systems

Entropically Driven Partitioning of Ethylene Oxide Oligomers and Polymers in Aqueous/Organic Biphasic Systems

Thermodynamics of the partitioning of poly(propylene oxide) between aqueous and chlorinated organic phases compared to poly(ethylene oxide) and other hydrophilic polymers

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