The Kinetic Length

The second quantity is the kinetic length, Lk, and measures the average separation between growth patches in the polynucleation regime. From Eq. (3.14) ... 

There is, however, serious doubt that 4 pm is the kinetic length of an individual chain. Consider a monomer crystal that contains a fraction Xo of short chains consisting of no repeat units. The average number of monomers enclosed between the ends of two polymer chains in a row and available for subsequent photopolymerization is ... 

The member kp[M]//Ct(i i)[Ro] has the meaning of the kinetic length of chains Vq = C which would be formed under identical conditions, but in a system where termination is independent of macroradical length. 

For this system the back reaction rate constant for the kinetic length, X], is k 2 "t he overall quan-... 

If termination occurs by coupling of the free radicals and still in absence of transfer, the number average degree of polymerization corresponds to twice the kinetic length ... 

At first we tried to explain the phenomenon on the base of the existence of the difference between the saturated vapor pressures above two menisci in dead-end capillary [12]. It results in the evaporation of a liquid from the meniscus of smaller curvature ( classical capillary imbibition) and the condensation of its vapor upon the meniscus of larger curvature originally existed due to capillary condensation. We worked out the mathematical description of both gas-vapor diffusion and evaporation-condensation processes in cone s channel. Solving the system of differential equations for evaporation-condensation processes, we ve derived the formula for the dependence of top s (or inner) liquid column growth on time. But the calculated curves for the kinetics of inner column s length are 1-2 orders of magnitude smaller than the experimental ones [12]. 

A striking feature of the images is the nonunifonnity of the distribution of the adsorbed species. The reaction between O and CO takes place at the boundaries between the surface domains and it was possible to detennine reaction rates by measuring the change in length L of the boundaries of the O islands. The kinetics is represented by the rate equation... 

As with the rate of polymerization, we see from Eq. (6.37) that the kinetic chain length depends on the monomer and initiator concentrations and on the constants for the three different kinds of kinetic processes that constitute the mechanism. When the initial monomer and initiator concentrations are used, Eq. (6.37) describes the initial polymer formed. The initial degree of polymerization is a measurable quantity, so Eq. (6.37) provides a second functional relationship, different from Eq. (6.26), between experimentally available quantities-n, [M], and [1]-and theoretically important parameters—kp, k, and k. Note that the mode of termination which establishes the connection between u and hj, and the value of f are both accessible through end group characterization. Thus we have a second equation with three unknowns one more and the evaluation of the individual kinetic constants from experimental results will be feasible. 

The degree of polymerization in Eq. (6.41) can be replaced with the kinetic chain length, and the resulting expression simplified. To proceed, however, we must choose between the possibilities described by Eqs. (6.34) and (6.35). Assuming termination by disproportionation, we replace n, by v, using Eq. (6.37) ... 

The kinetic chain length u may also be viewed as merely a cluster of kinetic constants and concentrations which was introduced into Eq. (6.54) to simplify the notation. As an alternative, suppose we define for the purposes of this chapter a fraction p such that... 

The three-step mechanism for free-radical polymerization represented by reactions (6.A)-(6.C) does not tell the whole story. Another type of free-radical reaction, called chain transfer, may also occur. This is unfortunate in the sense that it complicates the neat picture presented until now. On the other hand, this additional reaction can be turned into an asset in actual polymer practice. One of the consequences of chain transfer reactions is a lowering of the kinetic chain length and hence the molecular weight of the polymer without necessarily affecting the rate of polymerization. 

The kinetic chain length has a slightly different definition in the presence of chain transfer. Instead of being simply the ratio Rp/R, it is redefined to be the rate of propagation relative to the rates of all other steps that compete with propagation specifically, termination and transfer (subscript tr) ... 

Since the first term on the right-hand side is the reciprocal of the kinetic chair length in the absence of transfer, this becomes... 

We shall consider these points below. The mechanism for cationic polymerization continues to include initiation, propagation, transfer, and termination steps, and the rate of polymerization and the kinetic chain length are the principal quantities of interest. 

Chain transfer reactions to monomer and/or solvent also occur and lower the kinetic chain length without affecting the rate of polymerization ... 

In writing Eqs. (7.1)-(7.4) we make the customary assumption that the kinetic constants are independent of the size of the radical and we indicate the concentration of all radicals, whatever their chain length, ending with the Mj repeat unit by the notation [Mj ], This formalism therefore assumes that only the nature of the radical chain end influences the rate constant for propagation. We refer to this as the terminal control mechanism. If we wished to consider the effect of the next-to-last repeat unit in the radical, each of these reactions and the associated rate laws would be replaced by two alternatives. Thus reaction (7. A) becomes... 

The overall effect, aside from the change in the polymer composition, is a decrease in the rate of monomer reaction, the kinetic chain length, and the polymer molecular weight (83). 

An important descriptor of a chain reaction is the kinetic chain length, ie, the number of cycles of the propagation steps (eqs. 2 and 3) for each new radical introduced into the system. The chain length for a hydroperoxide reaction is given by equation (10) where HPE = efficiency to hydroperoxide, %, and 2/ = number of effective radicals generated per mol of hydroperoxide decomposed. For 100% radical generation efficiency, / = 1. For 90% efficiency to hydroperoxide, the minimum chain length (/ = 1) is 14. 

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