| Abstract: | Under the conditions of polydental binding, metal ions couple azacrown ether links of the polymer, limiting segmental chain mobility and decreasing statistical weight of the states available for complex formation. According to the rate constant dependence on conversion extent two different regimes of the complex formation reaction may be given: 1) retardation resulting from decreasing reactivity, the measured rate constant decreases by a few orders of magnitude in the course of time; 2) retardation followed by increasing reactivity, the observed rate constant remains unchangeable. The process covering conformational nonequilibrium states of macromolecular coil makes it dependent on the system prehistory which violates the law of mass action. The couplings being labile, the instantaneous value of pseudomonomolecular rate constant of the reaction is a function of conversion extent on metal and is not dependent on absolute polymer uptake by metal. The reaction rate in each point does not depend only on reagents concentration ratio but also on the character of metal ion distribution along the polymer chain obtained to the given moment. At complex formation with “hard” couplings the increase of metal concentration makes the effective retardation of the process change, whereas initial parts of the kinetic curves remain practically the same. In this system pseudomonomolecular rate constant does not seem to be a function of conversion extent, but is defined by absolute quantity of the formerly bound metal. Formal application of the law of mass action in this case is useless, it is necessary to apply distribution function on reactivity. Unlike solid phase systems nonequivalent character of reaction sites in the polymer is of evolution character, i.e.it arises in the course of the reaction on the account of polymer coil conformation change. |
