Die adiabatische Kompressibilität von Polyelektrolyten: Bindung von Na+-Ionen an die mehrwertige Stelle der Polymerketten

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Die adiabatische Kompressibilit?t von Polyelektrolyten: Bindung von Na+-Ionen an die mehrwertige Stelle der Polymerketten

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Adiabatic compressibility of polyelectrolytes in aqueous solutions. II. Poly(4-vinyl-N-n-butylpyridinium bromide)

The adiabatic compressibility for two samples (F-1 with DP-3748 and F-2 with DP-2114) of poly(4-vinyl-N-n-butylpyridinium bromide) in aqueous solution has been determined from ultrasonic velocity and density data. The sample (F-1) with the higher degree of polymerization shows comparatively higher velocity and density in solution. However, the evidence for the difference in compressibility is not very decisive. The apparent molal volume ΦV₂ and apparent molal compressibility ΦK₂ for F-1 are found to be slightly higher than for F-2. In aqueous solution, the decrement of adiabatic compressibility per unit concentration, (β₁ ? β)/c, is found to be almost constant throughout the entire concentration range, whereas in the presence of excess added electrolyte (1.0M KBr solution), the compressibility decrement shows a decrease with dilution. The latter values are lower than those found in water, since the molecules, in the presence of excess electrolyte, are coiled up more and are less compressible. The ΦV₂ and ΦK₂ values in water are constant throughout the entire concentration range, as the free counterions formed on dissociation in the dilute region are not solvated and hence contribute little to the compressibility. On the other hand, in the presence of excess KBr (1.0M), the ΦV₂ and ΦK₂ values show a sharp decrease with increase of polyelectrolyte concentration and finally attain a constant value. This is explained by the fact that because of the formation of a charge-transfer complex between the bromide ion and the polycation, more than the equivalent number of bromide ions is bound, leaving free an equal amount of K⁺ ions which are solvated and cause the lowering of apparent volumes and compressibilities. Condensation of charges begins at a certain polyelectrolyte concentration, and no further increase of K⁺ ions is observed. A special situation arises in 0.1M KBr solution. The ΦV₂ and ΦK₂ values at first increase sharply with increase of polyelectrolyte concentration, but then level off to attain a constant value, at comparatively high concentration. In 2.0% poly(4-vinyl-N-n-butylpyridinium bromide) solution, the concentration of polymer repeat unit (0.08M) is almost equal to the concentration of the added electrolyte (0.1M KBr) used to suppress dissociation. As the polyelectrolyte concentration in 0.1M KBr solution is progressively decreased, more bromide ions are made available for forming the charge-transfer complex with the polycation, leaving the K⁺ ions free to contribute to the compressibility.     

Adiabatic Compressibility and Apparent Molal Volume of Ionic Monomers,Polymers, and Copolymers in Aqueous and Nonaqueous Solutions

Abstract

In this review we are primarily concerned with the use of apparent molal volume and apparent molal compressibility of polyelectrolytes along with their corresponding monomers in elucidating the ion-ion and ion-solvent interactions in aqueous and nonaqueous solutions. Though the main emphasis will be given to synthetic polyelectrolytes, the biochemical significant (natural) ones are not excluded altogether. It is hoped that this information will provide researchers with up-to-date knowledge of the subject matter and give a new impetus to further study on the subject. Most of the works on molal volumes and ultrasonic velocity measurements were confined up to the middle sixties to solutions of simple electrolytes. These works gave valuable information about the structure of solutions as well as about the fundamental properties of solutions.