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Unfortunately, the usual Fox-Li or Valnshteln modes do not form a complete set (see, eg, Sec 63 p 330, and Probs 104 and 105 of [607]), due to adoption of the Sommerfeld radiation condition (discussed in Section 92), which excludes incoming radiation from infinity In a semiclassical treatment, this is a problem only when excitation of the resonator by an external field is considered (see, eg, Chap 10 of [607]) With the quantized radiation field,.



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The excellent agreement of the two indicates the validity of the steady-state assumption The rate constants for propagation and termination have been determined for many monomers Table 3-11 lists values for some of the common monomers These data were based on rotating sector experiments The monomers have been listed in order of decreasing kp values (which does not necessarily correspond to the exact order of decreasing kt values) The order of kp values is discussed in Sec 6-3b, since kp is a function of both monomer reactivity and radical reactivity The reader is cautioned that there is often a considerable divergence in the literature for values of rate constants [Buback et al, 1988, 2002] One needs to examine the experimental details of literature reports to choose appropriately the values to be used for any needed calculations.

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4They had a small hole for the molecular beam to enter. But as Sommerfeld showed, as long as the dimensions of the hole are small in comparison with the wavelength of the maser, leakage of radiation through the hole is negligible. It is not so for optical frequencies. 5As mentioned in Section 6.2, when the photon round-trip time is much shorter than its lifetime in the cavity, the losses appear to be distributed evenly throughout the cavity rather than being concentrated at the semitransparent walls. 6 As far as the author knows.

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Apparently different values of a rate constant may be a consequence of experimental error, experimental conditions (eg, differences in conversion, solvent viscosity), or method of calculation (eg, different workers using different literature values of kd for 1=2 calculating Ri , which is subsequently used to calculate kp =kt from an experimental determination of Rp ) A prime purpose of the IUPAC Working Party on Modeling of Kinetics and Processes of Polymerization has been standardization of the experimental conditions and calculation methods for obtaining rate constants and other parameters Table 3-12 shows the PLP-SEC values of the propagation rate parameters for a number of monomers For many monomers there is good agreement between the values obtained from the rotating sector and PLP-SEC methods..

general arguments leading to the conclusion that a suitable quantum-mechanical wave equation should be first order in time (e.g., see Sec. 27 in [159]). Dirac factorized (3.19) to express it as the square of a relation linear in E. But instead of simply writing

intermolecular forces, for example, polyamides and polyesters, develop suf cient strength to be useful at lower molecular weights than polymers having weaker intermolecular forces, for example, polyethylene Properties other than strength also show a signi cant dependence on molecular weight However, most properties show different quantitative dependencies on molecular weight Different polymer properties usually reach their optimum values at different molecular weights Further, a few properties may increase with molecular weight to a maximum value and then decrease with further increase in molecular weight An example is the ability to process polymers into useful articles and forms (eg, lm, sheet, pipe, ber) Processability begins to decrease past some molecular weight as the viscosity becomes too high and melt ow too dif cult.

(3.25) which introduces the double sign 13 and nonlinear terms in E / c (the Taylor expansion of the square root has all even powers of E / c), Dirac wrote (3.26) with the constraint that the square of (3.26) must yield the Klein-Gordon equation (3.24)

Thus the practical aspect of a polymerization requires one to carry out the process to obtain a compromise molecular weight a molecular weight suf ciently high to obtain the required strength for a particular application without overly sacri cing other properties Synthesizing the highest possible molecular weight is not necessarily the objective of a typical polymerization Instead, one often aims to obtain a high but speci ed, compromise molecular weight The utility of a polymerization is greatly reduced unless the process can be carried out to yield the speci ed molecular weight The control of molecular weight is essential for the practical application of a polymerization process When one speaks of the molecular weight of a polymer, one means something quite different from that which applies to small-sized compounds Polymers differ from the smallsized compounds in that they are polydisperse or heterogeneous in molecular weight.

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