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is applicable to an analysis of polymerization depolymerization equilibria. G is the G of polymerization for the monomer and polymer in the appropriate standard states [Dainton and Ivin, 1950, 1958; Ivin, 2000]. The standard state for monomer is often taken as the pure monomer or a 1 M solution. The standard state for the polymer is usually the solid amorphous or slightly crystalline polymer or a solution that is 1 M in the repeat unit of the

wavefunction. Second. as we will see in Section 3.6, it makes the connection with the usual canonical quantization formalism become very simple.



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Fig. 3-14 Variation of kp [M] and kdp with temperature for styrene. After Dainton and Ivin [1958] (by permission of The Chemical Society, Burlington House, London).

An analogous equation holds for A. From these two equations we see that whenever IICl 2 differs from J1-2, F and A will vanish. So: . and A must be given by : .(IC)

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polymer. For an equilibrium situation G 0, Q K and Eq. 3-175 may be combined with Eq. 3-173 to yield

= 0 (IICI2 - J1-2) U(IC) ,

G H T S RT ln K 3-176

(3.62) (3.63)





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K Mn 1 1 Mn M M 3-177

Equation 3-178b shows the equilibium monomer concentration M c as a function of the reaction or ceiling temperature Tc . (Note that H in Eq. 3-178 can be replaced by H because the enthalpy change is independent of [M]. This is not the case for S since the entropy change is dependent on [M].) Since H is a negative quantity, the monomer concentration in equilibrium with polymer increases with increasing temperature, that is, a plot of M c versus 1=T is linear with a negative slope of H =R and intercept of S =R. This means that there is a series of ceiling temperatures corresponding to different equilibrium monomer concentrations. For any monomer solution of concentration M c there is a temperature Tc at which polymerization does not occur. (For each M c there is a corresponding plot analogous to Fig. 3-14, in which kdp kp M at its Tc .) Stated another way, the polymerization of a particular monomer solution at a particular temperature proceeds until

A(IC) = 0 (IICI2 -, J1-2) l:(IC),

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TABLE 3-16 Polymerization Depolymerization Equilibriaa Monomer Vinyl acetate Methyl acrylate Ethylene Styrene Methyl methacrylate a-Methylstyrene Isobutylene M c at 25 C 1 10 9 1 10 9 1 10 6 1 10 3 2.2 Tc for Pure Monomer ( C) 400 310 220 61 50

where U(IC) and l:(IC) are two quaternion functions of IC yet to be determined. The delta function forces IC always to have a quaternion modulus square of J1- 2. This gives rise to the dispersion relation [238]

a Data from Cook et al. [1958]; McCormick [1957]; Wall [1960]; Worsfold and Bywater [1957].

So for each k, we have two solutions: one with positive frequency,

equilibrium is established, that is, until the monomer concentration decreases to the M c value corresponding to that Tc temperature Thus higher initial monomer concentrations are required with increasing temperature in order to observe a net production of polymer before equilibrium is established There is an upper temperature limit above which polymer cannot be obtained even from pure monomer The reader is cautioned to note that the literature often appears to refer only to a singular Tc value the ceiling temperature It is clear from the discussion above that each monomer concentration has its own Tc value The apparent designation of a singular Tc value usually refers to the Tc for the pure monomer or in some cases to that for the monomer at unit molarity.

(3.64)

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