Thermodynamic considerations monomer solutions

An important part of the optimization process is the stabilization of the monomer-template assemblies by thermodynamic considerations (Fig. 6-11). The enthalpic and entropic contributions to the association will determine how the association will respond to changes in the polymerization temperature [18]. The change in free volume of interaction will determine how the association will respond to changes in polymerization pressure [82]. Finally, the solvent s interaction with the monomer-template assemblies relative to the free species indicates how well it will stabilize the monomer-template assemblies in solution [16]. Here each system must be optimized individually. Another option is simply to increase the concentration of the monomer or the template. In the former case, a problem is that the crosslinking as well as the potentially nonselective binding will increase simultaneously. In the... 

Application of Activity at cmc. The above consideration suggested us to propose a new treatment for ionic micelle formation. According to thermodynamics, the micelle-monomer equilibrium is achieved when the chemical potential of surfactant in the micelle is equal to that in the bulk solution. The free energy of micelle formation can be represented by the use of the critical micelle activity, cma, which is the activity of surfactant at the cmc, as... 

The anionic polymerization of 58 shows typical equilibrium polymerization behavior. From the temperature dependence of the equilibrium monomer concentration, the thermodynamic parameters for the polymerization of 58 in dimethyl sulfoxide were evaluated to be AHSS = -23.8 1.5 kJ/mol and ASss = — 71.5 + 4.2 kJ/mol deg (subscript ss refers to a solution state). [67] The ceiling temperature for 1 mol/L solution is about 60 °C. The enthalpy change in the polymerization of 58 is considerably larger than those for monocyclic lactams, pyrrolidone and piperidone, but no quantitative comparison of these data can be made, because the reported data refer to different experimental conditions. The significant entropy decrease in the polymerization is ascribable to the presence of the six-membered tetrahydropyran ring in the repeating unit. 

Attempt of correlating the molecular structures and experimental data, for example, cmc, and the thermodynamic parameters of micellization (enthalpy, entropy, and free energy), rests on the assumption that they have been calculated by a consistent procedure this point needs further consideration. At the outset, it should be noticed that there are systematic differences between the results, for example, the cmc, obtained by using distinct experimental techniques. The reason is that the function plotted (absorbance of micelle-solubilized dye, conductivity, surface tension, light scattering intensity, etc.) versus [surfactant] measures different averages of the various species in solution. Examples are surface tension that primarily depends on monomer concentration and solubilization of (water-insoluble) dye that depends mainly on the total amount of micelles present. The consequence is that cmc measured from surface tension will always be lower than cmc measured by dye solubilization [28]. In fact, values of the cmc of the same surfactant, determined by different groups, by the same technique show differences. For example, fifty-four erne s determined by the same technique for Cj NMe Br (measurements at 25°C) differ by 22% [29]. 

The principal question arising in investigating the thermodynamic behavior of systems containing chemically different polymers or copolymers concerns the role of interactions between unlike monomers. In this respect, the consideration of dilute solutions provides useful information as it elucidates the importance of chain conformations and monomer concentration fluctuations. In a dilute solution of two polymers A and B the osmotic pressure may be approximated by a virial expansion limited to the second order ... 

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