Diffusion-Limited Phosphorescence Quenching Interactions in Polymer Solutions: Small Molecule-Small Molecule Interactions Interpreted by Free Volume Theory

Daniel H.S. Yu; John M. Torkelson

doi:10.1021/ma00182a032

Diffusion-Limited Phosphorescence Quenching Interactions in Polymer Solutions: Small Molecule-Small Molecule Interactions Interpreted by Free Volume Theory

Daniel H.S. Yu, John M. Torkelson^*

^*Corresponding author for this work

Chemical and Biological Engineering

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

Diffusion-limited interactions between benzil and anthracene were studied by phosphorescence quenching in polystyrene-cyclohexane, polystyrene-toluene, poly(methyl methacrylate)-toluene, and polybutadiene-cyclohexane solutions. Values of the bimolecular diffusion-limited quenching rate constant, k_q, were obtained by measuring benzil phosphorescence lifetime as a function of anthracene concentration and applying a Stern-Volmer analysis. Besides polymer species and solvent, k_qwas measured as a function of polymer molecular weight and concentration, up to 560 g/L. k_qwas found to be independent of polymer molecular weight in polystyrene-cyclohexane solutions and exhibited a slight molecular weight dependence in polystyrene-toluene solutions. The polymer concentration dependence of k_qin polystyrene-cyclohexane and polystyrene-toluene solutions was found to mimic the polymer concentration dependence of the solvent self-diffusion coefficient; this result is consistent with the notion that k_q~ D_S/D_S0where D_sis the solvent self-diffusion coefficient and the subscript 0 indicates the value at zero polymer concentration. A very similar polymer concentration dependence of k_qwas obtained in poly(methyl methacrylate)-toluene solutions. The Vrentas-Duda free volume theory for D_Swas found to predict the polymer concentration dependence of k_qquantitatively for polystyrene-toluene and approximately for poly(methyl methacrylate)-toluene solutions; over the range of polymer concentrations studied in polystyrene-cyclohexane solutions, the agreement between the Vrentas-Duda theory and experimental measures of k_qappears to be less satisfactory. The Fujita-Doolittle theory can also be used to fit experimental measures of k_qin selected cases; however, it is possible to obtain unphysical results if the Fujita-Doolittle theory is applied over too wide a range in polymer concentration.

Original language	English (US)
Pages (from-to)	1033-1041
Number of pages	9
Journal	Macromolecules
Volume	21
Issue number	4
DOIs	https://doi.org/10.1021/ma00182a032
State	Published - 1988

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/ma00182a032

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@article{a6ee375535424807a1e47ab161a33028,

title = "Diffusion-Limited Phosphorescence Quenching Interactions in Polymer Solutions: Small Molecule-Small Molecule Interactions Interpreted by Free Volume Theory",

abstract = "Diffusion-limited interactions between benzil and anthracene were studied by phosphorescence quenching in polystyrene-cyclohexane, polystyrene-toluene, poly(methyl methacrylate)-toluene, and polybutadiene-cyclohexane solutions. Values of the bimolecular diffusion-limited quenching rate constant, kq, were obtained by measuring benzil phosphorescence lifetime as a function of anthracene concentration and applying a Stern-Volmer analysis. Besides polymer species and solvent, kqwas measured as a function of polymer molecular weight and concentration, up to 560 g/L. kqwas found to be independent of polymer molecular weight in polystyrene-cyclohexane solutions and exhibited a slight molecular weight dependence in polystyrene-toluene solutions. The polymer concentration dependence of kqin polystyrene-cyclohexane and polystyrene-toluene solutions was found to mimic the polymer concentration dependence of the solvent self-diffusion coefficient; this result is consistent with the notion that kq~ DS/DS0where Dsis the solvent self-diffusion coefficient and the subscript 0 indicates the value at zero polymer concentration. A very similar polymer concentration dependence of kqwas obtained in poly(methyl methacrylate)-toluene solutions. The Vrentas-Duda free volume theory for DSwas found to predict the polymer concentration dependence of kqquantitatively for polystyrene-toluene and approximately for poly(methyl methacrylate)-toluene solutions; over the range of polymer concentrations studied in polystyrene-cyclohexane solutions, the agreement between the Vrentas-Duda theory and experimental measures of kqappears to be less satisfactory. The Fujita-Doolittle theory can also be used to fit experimental measures of kqin selected cases; however, it is possible to obtain unphysical results if the Fujita-Doolittle theory is applied over too wide a range in polymer concentration.",

author = "Yu, {Daniel H.S.} and Torkelson, {John M.}",

year = "1988",

doi = "10.1021/ma00182a032",

language = "English (US)",

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pages = "1033--1041",

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T1 - Diffusion-Limited Phosphorescence Quenching Interactions in Polymer Solutions

T2 - Small Molecule-Small Molecule Interactions Interpreted by Free Volume Theory

AU - Yu, Daniel H.S.

AU - Torkelson, John M.

PY - 1988

Y1 - 1988

N2 - Diffusion-limited interactions between benzil and anthracene were studied by phosphorescence quenching in polystyrene-cyclohexane, polystyrene-toluene, poly(methyl methacrylate)-toluene, and polybutadiene-cyclohexane solutions. Values of the bimolecular diffusion-limited quenching rate constant, kq, were obtained by measuring benzil phosphorescence lifetime as a function of anthracene concentration and applying a Stern-Volmer analysis. Besides polymer species and solvent, kqwas measured as a function of polymer molecular weight and concentration, up to 560 g/L. kqwas found to be independent of polymer molecular weight in polystyrene-cyclohexane solutions and exhibited a slight molecular weight dependence in polystyrene-toluene solutions. The polymer concentration dependence of kqin polystyrene-cyclohexane and polystyrene-toluene solutions was found to mimic the polymer concentration dependence of the solvent self-diffusion coefficient; this result is consistent with the notion that kq~ DS/DS0where Dsis the solvent self-diffusion coefficient and the subscript 0 indicates the value at zero polymer concentration. A very similar polymer concentration dependence of kqwas obtained in poly(methyl methacrylate)-toluene solutions. The Vrentas-Duda free volume theory for DSwas found to predict the polymer concentration dependence of kqquantitatively for polystyrene-toluene and approximately for poly(methyl methacrylate)-toluene solutions; over the range of polymer concentrations studied in polystyrene-cyclohexane solutions, the agreement between the Vrentas-Duda theory and experimental measures of kqappears to be less satisfactory. The Fujita-Doolittle theory can also be used to fit experimental measures of kqin selected cases; however, it is possible to obtain unphysical results if the Fujita-Doolittle theory is applied over too wide a range in polymer concentration.

AB - Diffusion-limited interactions between benzil and anthracene were studied by phosphorescence quenching in polystyrene-cyclohexane, polystyrene-toluene, poly(methyl methacrylate)-toluene, and polybutadiene-cyclohexane solutions. Values of the bimolecular diffusion-limited quenching rate constant, kq, were obtained by measuring benzil phosphorescence lifetime as a function of anthracene concentration and applying a Stern-Volmer analysis. Besides polymer species and solvent, kqwas measured as a function of polymer molecular weight and concentration, up to 560 g/L. kqwas found to be independent of polymer molecular weight in polystyrene-cyclohexane solutions and exhibited a slight molecular weight dependence in polystyrene-toluene solutions. The polymer concentration dependence of kqin polystyrene-cyclohexane and polystyrene-toluene solutions was found to mimic the polymer concentration dependence of the solvent self-diffusion coefficient; this result is consistent with the notion that kq~ DS/DS0where Dsis the solvent self-diffusion coefficient and the subscript 0 indicates the value at zero polymer concentration. A very similar polymer concentration dependence of kqwas obtained in poly(methyl methacrylate)-toluene solutions. The Vrentas-Duda free volume theory for DSwas found to predict the polymer concentration dependence of kqquantitatively for polystyrene-toluene and approximately for poly(methyl methacrylate)-toluene solutions; over the range of polymer concentrations studied in polystyrene-cyclohexane solutions, the agreement between the Vrentas-Duda theory and experimental measures of kqappears to be less satisfactory. The Fujita-Doolittle theory can also be used to fit experimental measures of kqin selected cases; however, it is possible to obtain unphysical results if the Fujita-Doolittle theory is applied over too wide a range in polymer concentration.

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JF - Macromolecules

IS - 4

ER -

Diffusion-Limited Phosphorescence Quenching Interactions in Polymer Solutions: Small Molecule-Small Molecule Interactions Interpreted by Free Volume Theory

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