Gas−Liquid Chromatographic Study of the Solution Thermodynamics of Hydroxylic Derivatives in Selected Polymeric Liquids

Huang, Jan‐Chan; Langer, Stanley H.; Sheehan, Richard J.

doi:10.1021/jp0366163

Cited by 8 publications

(25 citation statements)

References 69 publications

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“…In the IGC system, the solvent is usually nonvolatile and solutes are volatile with more free volume. The free volume effect is most noticeable in this type of system 24, 25. When χ h is considered, eq.…”

Section: Free Volume Effect In Enthalpy Of Sorptionmentioning

confidence: 93%

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Estimation of solubility parameter components of solutes and polymers using heat of vaporization and heat of sorption of solutes

Huang

2009

J of Applied Polymer Sci

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In a recent study, a two-dimensional solubility parameter model was used to correlate the heat of solution for solutes ranging from n-alkanes to alcohols, dissolved in isotatic polypropylene (PP), poly(ethyl ethylene) (PEE), and poly(dimethylsiloxane) (PDMS). When literature data of solubility parameter components of solutes were used, the correlation had some scattering for solutes with low values of cohesive energy density. In this study, the components of solubility parameters of solutes and polymers were estimated from cohesive energy and heat of sorption of solutes. Good correlation was obtained for the specific heat of sorption (DU sorp /V) for solutes ranging from n-alkanes to alcohols, and PDMS had a polar component as previously estimated. Free volume effect in solution process may be the source of a small systematic deviation from the model.

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Section: Free Volume Effect In Enthalpy Of Sorptionmentioning

confidence: 93%

“…The free volume effect is most noticeable in this type of system. 24,25 When v h is considered, eq. (8) becomes the following:…”

Section: Free Volume Effect In Enthalpy Of Sorptionmentioning

confidence: 99%

Estimation of solubility parameter components of solutes and polymers using heat of vaporization and heat of sorption of solutes

Huang

2009

J of Applied Polymer Sci

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“…12,13 For some solutes, data were not measured for 80°C because of lengthy retention time; for these, high-temperature data 36,37 were used to obtain ∆H h e ∞ and ∆S h re ∞ , and results were adjusted to 90°C using eq 3. The slopes and correlation coefficients (R) of S vs H , and vs H plots were determined and results are shown in Table 2.…”

Section: Solute State Interactionsmentioning

confidence: 99%

“…This has been discussed by Li and Carr 26 and Vailaya and Horváth 27,28 and is also found in our previous work. 13 The second possibility, which we propose in this study, arises when the solvent has a homogeneous molecular structure dominated by one type of interaction. The solution properties represent the difference in interactions between solute and solvent states.…”

Section: Introductionmentioning

confidence: 99%

Entropy−Enthalpy Compensations in Solutions of Dual Character Molecules with Polymeric Chromatographic Liquid Phases

2005

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Careful gas chromatographic studies provide thermodynamic data for insights into solution processes in nonvolatile solvents. Using 24 solutes and five stationary phases, several entropy-enthalpy compensation effects in the thermodynamics of solution were identified. Despite solute structure differences, when excess enthalpy and entropy of solutions were examined, entropy-enthalpy compensation effects were found in solvents dominated by single types of interaction: squalane and, to some extent, methoxy poly(ethylene oxide) (PEO). The main reason for the absence of linearity in other solvents is pure solute state interactions in the reference state and the multicharacter nature of solvents. In this study, consideration of solute state interactions was removed through examination of the thermodynamics of transfer between solvent pairs. It was found that solute transfers from squalane to poly[methyl(trifluoropropyl)siloxane] (QF-1) and to poly(methylphenyl) (DC-550) also gave linear relationships. The former system contains a second correlation for ester type solutes. The transfer data for squalane to poly(methylsiloxane) (DC-200) had smaller ranges and were more scattered. The effects of derivatizing groups on the transfer enthalpy and entropy were treated as a summation of hydrocarbon cores with the derivative groups. The group properties of transfer then also show entropy-enthalpy compensation effects. Many solution effects could be explained on the basis of solvent composition and local interactions with solutes.

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“…1,2 Among them inverse gas chromatography (IGC) is an effective tool for measuring the thermodynamic properties of solute (probe) vapors in high molecular weight polymers, particularly at the infinite dilution state. [3][4][5][6][7][8] From sorption data of low molecular weight solutes in polymers at several temperatures one can obtain the enthalpy and entropy of the solution process. In a recent study Huang et al 9 showed that linear entropy-enthalpy relationship was observed in IGC study of solutes in a nonpolar hydrocarbon solvent and a polar polyethylene oxide solvent.…”

Section: Introductionmentioning

confidence: 99%

Entropy–enthalpy compensation in solution properties of solutes at infinite dilution in nonpolar polymers

Huang

2007

J of Applied Polymer Sci

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The knowledge of the Flory-Huggins interaction parameter, w, between organic liquids and polymers is very important in the study of their miscibility. From the temperature dependency of w the enthalpy and residual entropy of solution can be determined. In this study literature data of thirty-two solutes, ranging from alkanes to alcohols, at infinite dilution in isotatic polypropylene, poly(ethyl ethylene), and poly(dimethylsiloxane), were tested and linear entropy-enthalpy compensation was observed. The plot of residual free energy versus enthalpy of solution was also linear, with a lower correlation coefficient than the entropyenthalpy plot. The range of enthalpy of solution was wider than those of the size corrected free energy of solution. In nonpolar solvents the enthalpy of solution reflected largely the interaction within the solute liquid state, and showed a linear trend with respect to solute cohesive energy density for n-alcohols. The wide range of enthalpy of solution suggests the use of a two-dimensional solubility parameter model to correlate the enthalpy of solution.

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Gas−Liquid Chromatographic Study of the Solution Thermodynamics of Hydroxylic Derivatives in Selected Polymeric Liquids

Cited by 8 publications

References 69 publications

Estimation of solubility parameter components of solutes and polymers using heat of vaporization and heat of sorption of solutes

Estimation of solubility parameter components of solutes and polymers using heat of vaporization and heat of sorption of solutes

Entropy−Enthalpy Compensations in Solutions of Dual Character Molecules with Polymeric Chromatographic Liquid Phases

Entropy–enthalpy compensation in solution properties of solutes at infinite dilution in nonpolar polymers

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