Gas-chromatographic study of the solution thermodynamics of hydroxylic derivatives and related compounds

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

doi:10.1021/j100220a029

Cited by 25 publications

(60 citation statements)

References 7 publications

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“…The Flory-Huggins interaction parameter represents the size-corrected free energy of solution and is calculated as RT. 10 The enthalpy of solution is calculated based on eq. (2) as…”

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confidence: 99%

Concentration dependency of interaction parameter between PVC and plasticizers using inverse gas chromatography

Huang

Deanin

2003

J of Applied Polymer Sci

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The inverse gas chromatography method was extended to study the concentration dependent FloryHuggins interaction parameter between poly(vinyl chloride) (PVC) and plasticizers using literature data. For both PVC/ polyadipate and PVC/epoxidized soybean oil (ESO) systems, the miscibility was better at the high PVC end. The specific interaction between PVC and plasticizers was estimated from the difference between the experimental results and the enthalpies of mixing predicted by the solubility parameter model. The interaction was negative and skewed toward the high PVC end, and rendered the overall interaction parameter negative at high PVC compositions. Chemical potential was used to determine the phase composition of PVC/plasticizer mixtures.

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“…The Flory-Huggins interaction parameter represents the size-corrected free energy of solution and is calculated as RT. 10 The enthalpy of solution is calculated based on eq. (2) as…”

mentioning

confidence: 99%

Concentration dependency of interaction parameter between PVC and plasticizers using inverse gas chromatography

Huang

Deanin

2003

J of Applied Polymer Sci

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“…This increase was more important for aromatic compounds and was supposedly caused by the increase in the electronic density, and hence the polarity, of the aromatic compounds. Activity coefficients at infinite dilution for squalane were less than one; these low values suggest low solution enthalpies for the methyl-alkane interactions, as found by Langer et al (1982). It can also be observed that this value increased as the size of solute increased.…”

Section: Resultsmentioning

confidence: 57%

Determination of solubility parameters and thermodynamic properties in hydrocarbon-solvent systems by gas chromatography

Dı́az

Cazurro

Ordóñez

et al. 2007

Braz. J. Chem. Eng.

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-Gas chromatography used to calculate the specific retention volume of several hydrocarbons in different chromatographic liquid phases (Squalane, Carbowax-400, Carbowax-1500, Carbowax-4000, Amine-220, Dinonyl phthalate, Tributyl phosphate and Trixylenyl phosphate). Some thermodynamic parameters, such as enthalpy of sorption and Flory-Huggins parameters relating the interaction between liquid phases and solutes, were also calculated from the determined retention volumes. Liquid phase solubility parameters of Squalane, Carbowax-400, Carbowax-1500 and Carbowax-4000 at 80 ºC as well as the polar and apolar components were calculated too. A new model was proposed to correlate polar contribution to the solubility parameter of a liquid phase with the specific retention volume of a solute in this liquid phase.

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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%

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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Gas-chromatographic study of the solution thermodynamics of hydroxylic derivatives and related compounds

Cited by 25 publications

References 7 publications

Concentration dependency of interaction parameter between PVC and plasticizers using inverse gas chromatography

Concentration dependency of interaction parameter between PVC and plasticizers using inverse gas chromatography

Determination of solubility parameters and thermodynamic properties in hydrocarbon-solvent systems by gas chromatography

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

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