Sorption, Dilation, and Isothermal Glass Transition of Poly(ethyl methacrylate)-Organic Gas Systems

Kamiya, Yuichi; Bourbon, Dominique; Mizoguchi, Keishin; Naito, Yasutoshi

doi:10.1295/polymj.24.443

Cited by 23 publications

(23 citation statements)

References 21 publications

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“…In the Henry's law (i.e., low concentration) region, Equation 1 becomes The Henry's coefficients for the dissolution ( K D ) and hole‐filling domains ( b Q ), as well as the affinity coefficient for the hole‐filling domain ( b ), each correlate with the octanol—water partition coefficient K ow (Eqns. 9–11; values in parentheses represent the standard error), consistent with solvophobic effects as an important driving force for sorption in each domain. Note that the K ow values were obtained from Schwarzenbach et al [15]: One can see by inspection of Equations 9 and 10 and the ratio bQ/K D given in Table 1 that solid‐phase dissolution is intrinsically much weaker than hole‐filling in all cases.…”

Section: Resultssupporting

confidence: 57%

“…This particle configuration was observed for two similar polymeric sorbents, XAD-2 and XAD-4 (Rohm and Haas, Philadelphia, PA, USA) [7]. Based on classical polymer theory [8][9][10][11][12], the glassy polymer is a Fig. 1.…”

Section: Introductionmentioning

confidence: 68%

“…The simple dual‐mode model (DMM) isotherm for a single solute takes the form where q eq (M M −1 ) is the equilibrium sorption, C eq (M L −3 ) is the equilibrium solute concentration, K D (L 3 M −1 ) is the partition coefficient between solution and the (linear) dissolution domain of Tenax, and b (L 3 M −1 ) and Q (M M −1 ) are, respectively, the Langmuir affinity and capacity coefficients for adsorption in the hole‐filling domain. Kamiya et al [10] introduced the extended DMM (EDMM) that takes into account plasticization (i.e., softening) by the sorbate, which converts the polymer from glassy to rubbery, completed at the glass‐transition concentration S g . Plasticization causes an inflection in the isotherm.…”

Section: Methodsmentioning

confidence: 99%

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Model‐aided characterization of Tenax®‐ta for aromatic compound uptake from water

Pignatello

2004

Enviro Toxic and Chemistry

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The polymer adsorbent Tenax has been widely employed for studying desorption of organic contaminants in soils and sediments and for correlating physical availability with bioavailability. Although Tenax has been invoked to act as an infinite sink that completely and instantaneously removes solutes from the aqueous phase, to our knowledge no systematic characterization of Tenax resins has been carried out. The present study provides equilibrium and kinetic parameters for the uptake of benzene, nitrobenzene, naphthalene, phenanthrene, and pyrene by Tenax in selected water-solute-Tenax systems, and it offers guidelines for the use of Tenax resins. Sorption isotherms of the test compounds on Tenax-TA are nonlinear, and most show an inflection at high concentration, marking a change in physical state from glassy to rubbery. A simple dual-mode model was applied to the isotherms below the apparent inflection point. Sorption parameters for dissolution and hole-filling domains each correlate with the octanol-water partition coefficient. The effects of dissolved organic matter and salinity on Tenax-TA uptake are minor. Regeneration of Tenax-TA by hot-methanol extraction increased its affinity for naphthalene. Inclusion of 23% graphitized carbon in the polymer reduced affinity for phenanthrene. Uptake rate data were fit by the dual-mode diffusion model, which assumes diffusion in the polymer matrix. The obtained diffusion rate parameter correlates with molecular size. Equilibrium and kinetic parameters for benzene and nitrobenzene were comparable despite a three-orders-of-magnitude difference in their Henry's law coefficients, indicating that a pathway to the Tenax surface through the vapor phase is not required. Extrapolating to typical conditions in soil-desorption studies reveals that single-solute uptake is 95% or more complete within 4 min for the test compounds and within 7 min for benzo[a]pyrene. Thus, Tenax is suitable for compounds with desorption from soil or sediment that occurs over comparably longer timescales.

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Section: Resultssupporting

confidence: 57%

Section: Introductionmentioning

confidence: 68%

Section: Methodsmentioning

confidence: 99%

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Model‐aided characterization of Tenax®‐ta for aromatic compound uptake from water

Pignatello

2004

Enviro Toxic and Chemistry

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“…In addition, prior work by this author and others has shown that organic solvents can increase the sorption-desorption kinetics of HOCs on soils and sediments [11,13], thus implying that solvents change the NOM character in some way that facilitates HOC exchange. Recent work on the effect of the cosolvent methanol on sorption isotherm linearity was consistent with the NOM rubbery/glassy polymer conceptualization [18], i.e., the presence of methanol in NOM increased isotherm linearity as solvents do in synthetic polymers [19,20]. So some evidence exists that cosolvents can affect the sorptive character of NOM.…”

Section: Introductionsupporting

confidence: 60%

Cosolvent effects of phenanthrene sorption‐desorption on a freshwater sediment

Bouchard

2003

Enviro Toxic and Chemistry

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Abstract-This study evaluated the effects of the water-miscible cosolvent methanol on the sorption-desorption of phenanthrene by the natural organic matter (NOM) of a freshwater sediment. A biphasic pattern was observed in the relationship between the log of the carbon-normalized sorption distribution coefficient (K oc ) and the volumetric fraction of water-miscible cosolvent (f c ), in this case methanol, that was accounted for with phenanthrene solubility data. Results also indicated that methanol elicited additional effects on phenanthrene sorption beyond the solution phase effects. The level of f c was observed to have a significant effect on sorption-desorption hysteresis, with hysteresis being greater for treatments where phenanthrene and sediment were equilibrated with methanol-phenanthrene solutions but desorbed with aqueous solutions. These results are discussed in light of the deformable pore network of the rubbery/glassy NOM polymer construct.

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“…Partial molar volume of C02 in different polymers; references are literature values(34)(35)(36)(37)(38)(39)(40) …”

mentioning

confidence: 99%

Transport of gases through polymeric membranes

Weßling

Boomgaard

Mulder

et al. 1993

Makromolekulare Chemie. Macromolecular Symposia

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In this paper tailor‐made polymers like polyoxadiazoles, polytriazoles and polyimides are compared with conventional polymers as gas separation membrane materials. Because their permeation characteristics as a function of the free volume does not compare too well with that of the conventional ones the term free volume was reconsidered. Based on a unique relation between the diffusion coefficient and the jump of the heat capacity at the glass transition temperature Tg, the transport mechanism in the polymer matrix is considered to occur in jump motions from one cavity to an adjacent one. This mechanism was reconfirmed by a molecular dynamics study. It is shown that mass transport at high penetrant concentrations is not time‐independent but a phenomenon with transient characteristics. This transient character is also found in the volumetric behaviour during sorption. The polymer matrix is described as a network with topological constraints which changes its state upon high swelling stresses induced by the sorbed penetrant.

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Sorption, Dilation, and Isothermal Glass Transition of Poly(ethyl methacrylate)-Organic Gas Systems

Cited by 23 publications

References 21 publications

Model‐aided characterization of Tenax®‐ta for aromatic compound uptake from water

Model‐aided characterization of Tenax®‐ta for aromatic compound uptake from water

Cosolvent effects of phenanthrene sorption‐desorption on a freshwater sediment

Transport of gases through polymeric membranes

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