Polyelectrolytes dissociation

Polyelectrolytes (most notably ionic cellulose derivatives and crosslinked polyacid powders) are also commonly used as matrices, binders and excipients in oral controlled release compositions. In these applications, the polyelectrolytes provide hydrophilicity and pH sensitivity to tablet dosage forms. Acidic polyelectrolytes dissociate and swell (or dissolve) at high pH values whereas basic polyelectrolytes (for instance, polyamines) become protonated and swell at low pH. In either case, swelling results in increased permeability [290], thereby allowing an incorporated drug to be released. 

One consequence of dealing with polyelectrolytes and naturally occurring ionisable macromolcules is that it is necessary to know the extent of ionisation before osmotic data can be interpreted. For example, suppose the sodium salt of a polyelectrolyte dissociates into u sodium ions and the single polyanion Pv, then the van t Hoff equation read... 

The dissociation state of a weak PE directly affects the complexation ability and the composition of the resultant PEC. - It was observed that a low pH may lead to suppression of polyelectrolyte dissociation, thereby leading to no complex formation. Increasing the pH increased the ionic strength, dissociation, and complex formation. Higher pH and ionic strength will lead to complete dissociation of polyion and an equimolar PEC coacervate will be obtained. 

A species (e.g., a colloidal particle or a flexible chain) that is partially ionizable when placed in a solution. The polyelectrolyte dissociates into a macroion and counterions. 

Extending the Henderson-Hasselbalch equation for a polyelectrolyte containing weak acid units, the negative logarithm pifapp of an apparent polyelectrolyte dissociation constant i app can be determined from titration measurements using the following definition (186) ... 

Since the polyelectrolyte dissociation releases counter-ions, this affects the solution s ionic strength and consequently the Debye length (distance over which significant charge separation can occur). The Debye length (in nm) can be expressed as ... 

The parameter n reflects the measure of deviation of the system from the behavior of the monomeric acid where n = 1, i.e., it characterizes the degree of interaction between the neighboring functional groups of the macroion. The value of n depends on the structure of the polyelectrolyte and the nature of the counterion pK = pK0 — log (1 — a)/a is the negative decadic logarithm of the effective dissociation constant of the carboxylic CP depending on a. 

This potential reflects itself in the titration curves of weak polyacids such as poly(acrylic acid) and poly(methacrylic acid) [32]. Apparent dissociation constants of such polyacids change with the dissociation degree of the polyacid because the work to remove a proton from the acid site into the bulk water phase depends on the surface potential of the polyelectrolyte. 

The salt effect is very strong in polyconjugated polyelectrolytes. Figure 15 is a graph of the proton dissociation energy vs. the dissociation degree of PPA of different structures. Also, the graphs for poly(methacrylic acid) and a copolymer... 

Fig. 15. Energy of proton dissociation (Ez) from Z times ionized polyelectrolyte molecules as function of the degree of dissociation (a). (A) - PPAL (1), PPAS (2), PPA (3), polyfmethacrylic acid) (4), copolymer of acrylic acid with ethylenesulfonic acid (50 50) in aqueous solutions (5), (B) - PPAL (1), PPAS (2), PPA in the presence of NaCl (3) ( ) INaClj = 0 (X) fNaCll = 0.25 mmol/1 (o) 0.50 mmol/1...

Polyelectrolyte complexes composed of various weight ratios of chitosan and hyaluronic acid were found to swell rapidly, reaching equilibrium within 30 min, and exhibited relatively high swelling ratios of 250-325% at room temperature. The swelling ratio increased when the pH of the buffer was below pH 6, as a result of the dissociation of the ionic bonds, and with increments of temperature. Therefore, the swelling ratios of the films were pH-and temperature-dependent. The amount of free water in the complex films increased with increasing chitosan content up to 64% free water, with an additional bound-water content of over 12% [29]. 

Note that when the concentration of added salt is very low, Debye length needs to be modified by including the charge contribution of the dissociating counterions from the polyelectrolytes. Because the equilibrium interaction is used, their theory predicts that the intrinsic viscosity is independent of ion species at constant ionic strength. At very high ionic strength, the intrachain electrostatic interaction is nearly screened out, and the chains behave as neutral polymers. Aside from the tertiary effect, the intrinsic viscosity will indeed be affected by the ionic cloud distortion and thus cannot be accurately predicted by their theory. 

Extensive data are given in the Uterature for the potentiometric titration of polymer acids which may be used to study the behaviour of polyelectrolyte systems under different conditions. For poly(a-D) galacturonic acid there are few data of this kind, especially in connection with the occurrence of a conformational transition induced by pH variations, or with the effect brought about by the addition or the exchange of counterions. Since for a polyacid not exhibiting a conformational transition in the course of titration, pK K denoting the apparent dissociation constant) increases monotonously with degree... 

Polyelectrolytes are polymers having a multiplicity of ionizable groups. In solution, they dissociate into polyions (or macroions) and small ions of the opposite charge, known as counterions. The polyelectrolytes of interest in this book are those where the polyion is an anion and the counterions are cations. Some typical anionic polyelectrolytes are depicted in Figure 4.1. Of principal interest are the homopolymers of acrylic acid and its copolymers with e.g. itaconic and maleic adds. These are used in the zinc polycarboxylate cement of Smith (1968) and the glass-ionomer cement of Wilson Kent (1971). More recently, Wilson Ellis (1989) and Ellis Wilson (1990) have described cements based on polyphosphonic adds. 

Solutions of polyelectrolytes contain polyions and the free (individual) counterions. The dissociation of a polyacid or its salt yields polyanions, and that of a polybase or its salt yields polycations, in addition to the simple counterions. The polyampholytes are amphoteric their dissociation yields polyions that have anionic and cationic functions in the same ion and often are called zwitterions (as in the case of amino acids having HjN and COO groups in the same molecule). Such an amphoter will behave as a base toward a stronger acid and as an acid toward a stronger base its solution properties (particularly its effective charge) will be pH dependent, and an isoelectric point (pH value) exists where anionic and cationic dissociation is balanced so that the polyion s charges add up to zero net charge (and solubility is minimal). 

By definition, in a solution all ions belong to the same phase, even though counterions may cluster more or less diffusely around the macroions. When significant amounts of a simple 1 1 electrolyte (such as KCl) are added to a polyelectrolyte solution, dissociation of the polyelectrolyte macromolecule is repressed in an extreme case the polyelectrolyte may be salted out. An undissociated polyacid may be precipitated by generous addition of a simple acid such as HCl. 

The viscosity and non-Newtonian flooding characteristics of the polymer solutions decrease significantly in the presence of inorganic salts, alkali silicates, and multivalent cations. The effect can be traced back to the repression of the dissociation of polyelectrolytes, to the formation of a badly dissociating polyelectrolyte metal complex, and to the separation of such a complex fi"om the polymer solution [1054]. 

Poly(starch-g-((l-amidoethylene)-co-(sodium 1-carboxylatoethylene))). Poly(l-amidoethylene) is, however, rarely used as a viscosifier. Instead, the homopolyraer is reacted with base (hydrolyzed with NaOH) to convert some of the amide units of the polymer to carboxylic acid units. The acid units on the hydrolyzed polymer dissociate in water and produce a polyanionic polymer. This polyelectrolyte expands in water because of ion-ion repulsion and, as an enlarged molecule, is a better viscosifier. 

Polyelectrolytes (Table 6) exhibit a large amount of dissociable groups. These compounds are often used for ion-exchange chromatography. They can also be used to exchange their counterions with indicator ions (see section 4). 

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