Titration, conductometric experimental methods

Many experimental approaches have been appHed to the deterrnination of stabihty constants. Techniques include pH titrations, ion exchange, spectrophotometry, measurement of redox potentials, polarimetry, conductometric titrations, solubiUty deterrninations, and biological assay. Details of these methods can be found in the Hterature (9,10). 

Provided the described experimental procedure is followed, there seems to be little restriction in the use of the analysis. Typical data obtained by conductometric titration for the sulfonate contents of a variety of pulps and lignin are shown in Table 7.7.1 along with data obtained by other methods. 

A discussion of the chemical drive of solvation and hydration processes, respectively, leads to the introduction of the basic concept of electrolytic dissociation, the disintegration of a substance in solution into mobile ions. Subsequently, we learn about the migration of these ions along an electric potential gradient as a special case of spreading of substances in space. The ionic mobilities provide a link to conductance and the related quantities conductivity as well as molar and ionic conductivity. For determining the conductivity of ions experimentally, the introduction of the term transport number which indicates the different contribution of ions to the electric current in electrolytes is very useful. In the last section, the technique for measuring conductivities is presented as well as its application in analytical chemistry where conductometric titration is a routine method. 

The experimental results may be represented both by the titration curves or property-composition dependences. The extremums or bends on the titration curves indicate the formation of complexes and their composition. Thus, investigating the-possi-bility of complex formation in polyelectrolyte - nonionic polymer systems, one can use the methods of conductometric and potentiometric titration. The formation of interpolymer complexes in these systems, as some authors suggest18,211, is caused by a co-operative formation of hydrogen bonds between carboxy groups of the polyacid and oxygen atoms of nonionic polyvinylpyrrolidone or poly(ethylene glycol) and is therefore accompanied by an increase of pH of the solution. The typical titration curves for the system polyvinylpyrrolidone - copolymer maleic anhydride and acrylic add are shown in Fig. 1. The inflection points of the titration curves indicate the ratio at which the macromolecular components react with each other, i.e. the composition of the formed complexes. 

The electromotoric force (emf) of a cell depends on the ionic concentration of the solutions. To locate the equivalence point, the variation in emf is monitored as the concentration of the analyte changes. When the measured emf is plotted against the total volume of titrant added, the curve produced is similar to that of a titration curve Fig. 4. This technique has all the advantages of the conductometric method and gives an experimental curve from which the endpoint can be detected accurately. 

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