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1-4 MOLECULAR WEIGHT The molecular weight of a polymer is of prime importance in the polymer s synthesis and application. Chemists usually use the term molecular weight to describe the size of a molecule. The more accurate term is molar mass, usually in units of g mol 1 . The term molecular 1 weight is the ratio of the average mass per formula unit of a substance to 12th of the mass of 12 an atom of C and is dimensionless (IUPAC, 1991, in press). This text will use molecular weight throughout irrespective of the units, because molecular weight is the more familiar term for most chemists. The interesting and useful mechanical properties that are uniquely associated with polymeric materials are a consequence of their high molecular weight. Most important mechanical properties depend on and vary considerably with molecular weight as seen in Fig. 1-3. There is a minimum polymer molecular weight (A), usually a thousand or so, to produce any signi cant mechanical strength at all. Above A, strength increases rapidly with molecular weight until a critical point (B) is reached. Mechanical strength increases more slowly above B and eventually reaches a limiting value (C). The critical point B generally corresponds to the minimum molecular weight for a polymer to begin to exhibit suf cient strength to be useful. Most practical applications of polymers require higher molecular weights to obtain higher strengths. The minimum useful molecular weight (B), usually in the range 5000 10,000, differs for different polymers. The plot in Fig. 1-3 generally shifts to the right as the magnitude of the intermolecular forces decreases. Polymer chains with stronger



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By default, Word is set to Insert mode: when you start typing, any existing text moves over to accommodate the new text. You can press to switch to Overtype mode, in which new text overwrites existing text.

There are two possible points of attachment on monosubstituted (X H) or 1,1-disubstituted monomers for a propagating radical on either carbon 1





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calculating how large the cosmological constant must be in order to explain these irregularities) [523] A more rigorous upper bound than that found in the preceding paragraph was obtained by Anderson et al [21] using data from the Voyager spacecraft to calculate the fractional change in period of Uranus and Neptune Their analysis shows that the energy density of the vacuum must be smaller than 10 14 GeV/m 3 To estimate the gravitational effect of the electromagnetic zero-point energy predicted by theory, we can adopt the Planck energy as a cutoff This is the energy at which the gravitational interaction becomes as strong as the other three fundamental forces of nature (ie, the scale at which we expect the current theory to break down) This energy is about 10 19 GeV.

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This yields a zero-point energy density of about 10 121 GeV/m 3 ; that is, the disagreement between this and the experimental upperbound derived in the preceding paragraph is of 107 orders of magnitude: the largest disagreement bet'feen theory and experiment ever seen in the history of physics! In analogy with the ultraviolet catastrophe of blackbody radiation that lead Planck to introduce his constant in physics, this has been called the vacuum catastrophe In 1967, Zeldovich [663] pointed out that the vacuum zero-point energy could account for the cosmological constant [483,629] The cosmological constant is a term that Einstein introduced to his field equations in 1917 when he was trying to apply them to the entire universe At that time it was generally believed that the universe would be static Without this constant term to counterbalance the gravitational attraction of matter, the universe would collapse.

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The connection between the vacuum zero-point energy and the cosmological constant is particularly relevant today, because in 1998 new astronomical observations revealed that the expansion of the universe is actually accelerating45 [482, 519, 538] These observations point to a vacuum zero-point energy of about 70% of the total energy density of the universe Unfortunately, this is still too low to be accounted for by the current fundamental field theory Some researchers consider the vacuum catastrophe a sign of the breakdown of our current physical theories, something that could only be resolved within the context of a bigger theory, where gravity and quantum mechanics would be unified [27]..

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To review the role of Poisson brackets in classical mechanics, see Goldstein's book [240]. You might also like to read Lanczos's interesting historical account [385] of the origins of the Poisson bracket and its introduction in quantum mechanics, as well as have a look at [62] and [143] . Our introduction to canonical quantization followed closely Dirac's own approach in [159]. For an account of how Dirac hit upon the idea of canonical quantization, there is nothing better than getting it straight "from the horse's mouth" in [158].

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