Morawetz

Morawetz E 1972 Enthalpies of vaporization of/i-alkanes from C, 2to C2q J. Chem. Thermodyn. 4 139... 

Morawetz, H. (1985) Polymers The Origins and Growth of a Science (Wiley-1 nterscience. New York republished in a Dover edition, 1995). 

As Morawetz puts the matter, an acceptance of the validity of the laws governing colligative properties (i.e., properties such as osmotic pressure) for polymer solutions had no bearing on the question whether the osmotically active particle is a molecule or a molecular aggregate . The colloid chemists, as we have seen, in regard to polymer solutions came to favour the second alternative, and hence created the standoff with the proponents of macromolecular status outlined above. 

At the end of the 1930s, the only generally available method for determining mean MWs of polymers was by chemical analysis of the concentration of chain end-groups this was not very accurate and not applicable to all polymers. The difficulty of applying well tried physical chemical methods to this problem has been well put in a reminiscence of early days in polymer science by Stockmayer and Zimm (1984). The determination of MWs of a solute in dilute solution depends on the ideal, Raoult s Law term (which diminishes as the reciprocal of the MW), but to eliminate the non-ideal terms which can be substantial for polymers and which are independent of MW, one has to go to ever lower concentrations, and eventually one runs out of measurement accuracy . The methods which were introduced in the 1940s and 1950s are analysed in Chapter 11 of Morawetz s book. 

The polyelectrolyte catalysis of chemical reactions involving ionic species has been the subject of extensive investigations since the pioneering studies of Morawetz et al. [12] and Ise et al. [13-17]. The catalytic effect or the ability of poly-electrolytes to enhance or retard reaction rates is mainly due to concentration or exclusion of either or both of the ionic reactants by the polyions added to the reaction systems. For example, the chemical reaction between ionic species carrying the same charge is enhanced in the presence of polyions carrying the opposite charge. This enhancement can be attributed to an increase in the local concentration... 

The modification of reaction rates by such a functionalized polyelectrolyte system was first made in 1959 by Ladenheim and Morawetz [23] in the Menshutkin... 

Ladenheim and Morawetz [23] also showed that the reactivity of the carboxylate units in partially ionized poly(methacrylic acid) (PMA) toward BrCH2COO in the bromine displacement reaction was greatly diminished, while the reaction proceeded at an appreciable rate with uncharged p-bromoacetamide [23]. This inhibition of the reaction of the polyanion with a small anionic reagent can be attributed to the electrostatic repulsion between the polymer and the reagent. 

Cationic polyelectrolytes containing imidazole groups have been investigated by some researchers. Morawetz et alU4 first found that a cationic polymer, poly (l-vinyl-3-ethylimidazolium iodide), 65 (PQMelm), enhanced the hydrolyses of the negatively charged esters, i. e. NABA and 4-acetoxy-3-nitrobenzenesulfonate 66 (NABS). At intermediate pH, a large catalytic effect was observed and this was... 

Kabanov etal.123 hydrolyzed 44 (PNPA) and 56 (NABA) in the presence of QPVP. They found that the hydrolysis rate decreased with increasing degree of quatemization in water. A bell-shaped dependence was observed for 56 (NABA) in alcohol-aqueous media (see Fig. 13). Recently, Cho and Morawetz discussed the hydrolyses of a polymer substrate by a pyridine-containing polymer124. ... 

Catalysis and Inhibition in Solutions of Synthetic Polymers and in Micellar Solutions H. Morawetz... 

Morawetz, H. (1975). Macromolecules in Solution, 2nd edn. Chapter 7. New York Wiley. 

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