PDC in the Dynamic Region

The calculation of the phenomenological function a(P T) of the flow-equilibrium from the measured calibration curves, shown in Figs. 7 and 8, is based on a nonlinear fit of Eq. (19) to these curves. It proceeds by the same method 4) as applied to the calculation of the reversible-thermodynamic data from Table 2 in Section 3.1 the phenomenological function a(P T), obtained in this way, is shown in Table 3 b. With this, the relative perturbation, 8Q/K, of the thermodynamic equilibrium by the transport can be calculated according to Eq. (20). 

The temperature dependence of the function 5Q/K is shown in Fig. 14 for four typical weight average degrees of polymerization, as indicated. The shape of these curves resembles the shape of the standard deviations cr of the corresponding elution curves, as shown in Fig. 153. This agreement represents a direct proof of the correctness of the flow-equilibrium concept proposed, because the function ct — crP = 0 represents an independent measure for the column resolution not based on any concept for the resolution mechanism. 

T o calculate all kinetic constants of the flow-equilibrium, only the (P, T)-dependence of the rate constant ks of a spontaneous polymer diffusion from the sol into the gel must be investigated independently. The rate constant kg of the reversible rediffusion of this P-mer from the gel into the sol follows from Eqs. (16b) and (4) and from Table 2, 

The rate constant k of the corresponding retarded rediffusion in the flow-equilibrium is obtained from Eqs. (21) and (20) and Table 3. The reduced axial rate x of the axial 

3 A rather complicated relationship between a(T) and P is, however, expressed in Fig. 15, because these curves are parametrized by a MWD w(P) as indicated, and not by a simple number, Pw, like those from Fig. 14 (cf. Sect. 5) 

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