This book presents direct and inverse gas chromatography as a powerful tool for determining a great number of thermodynamic properties and quantities for micro- and especially for macromolecular substances. In order to ensure the continuity and clarity of the presentation, the book first considers some frequently used concepts of chromatography with a mobile gas phase, i.e. the mechanism of separation, retention parameters and the theories of gas chromatography. The employment of this technique as an important method of studying solutions through the most representative statistical models is also discussed. The thermodynamics of direct gas chromatography, as applied to dissolution, adsorption and vaporization underlies the thermodynamic treatment of inverse gas chromatography. The most extensive chapter of the book is devoted to the thermodynamics of inverse gas chromatography and deals with a number of important topics: phase transitions in crystalline-amorphous polymers and liquid crystals, glass transitions, other second order transitions in polymers, the determination of diffusion coefficients, the segregation of block copolymers and other applications.

In this study, thermodynamic properties, namely retention volume, infinitely dilute weight fraction activity coefficient, Flory- Huggins interaction parameter, solubility parameters of solute and polymer, partition coefficient and diffusion coefficients of the various solvents in poly (methyl methacrylate co butyl methacrylate) (PMMA co BMA) and poly (lactide co glycolide) (PLGA) at infinite dilution of the solvent have been determined by inverse gas chromatography (IGC). In this technique, a small amount of the solvent was injected into the capillary column and its retention time was measured and used to calculate several polymer-solvent interaction parameters which are mentioned above. The solutes used in this study were methanol, ethanol, propanol, butanol, methyl acetate, ethyl acetate, propyl acetate, dichloromethane, trichloromethane, acetone, methyl methacrylate, butyl methacrylate, water for PMMA co BMA and acetone, dichloromethane, trichloromethane, ethyl acetate, ethyl alcohol, tetrahydrofuran, water for PLGA. The glass transition temperature of the polymers were determined as 106 0C and 42 0C for PMMA co BMA and PLGA respectively by differential scanning calorimetry. Experiments were performed in the range of 150-200 0C for PMMA co BMA and 80-120 0C for PLGA which are above the glass transition temperature of the polymer. The thermodynamic results, obtained from the experiments, indicated that trichloromethane and dichloromethane were the most suitable solutes among all the solvents studied for both of the polymers. The partition (K) and diffusion coefficients (Dp) of various solvents at infinite dilution of the solvent were calculated by using the model developed by Pawlisch et al. (1987). The optimum K and Dp values that best fit the data were found and the model predicted experimental data very well. In summary, IGC method is a powerful tool for the determination of thermodynamic and diffusion properties of solvent in polymer at infinite dilution of the solvent. Vrentas- Duda free volume theory was used to correlate the diffusion data and to investigate the effect of solvent size on diffusion process. The theory has shown to correlate diffusion data above the glass transition temperature very well for the PMMA-co-BMA .solvent system.

Polymer Thermodynamics by Gas Chromatography