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Table 2-10 shows the rate constants for the various reactions. It is apparent that there are signi cant differences in the reactivities of the different functional groups in phenol (i.e., in the different positions on the ring). The reaction between phenol and formaldehyde involves a nucleophilic attack by the phenolate anion on formaldehyde (Eq. 2-174) (or its hydrated form). The electron-pushing methylol groups generally increase the reactivity of phenol toward further substitution although steric hindrance modi es this effect. It is dif cult to quantitatively discuss the reasons for the speci c differences in reactivity, since there is no general agreement on even the relative values of the seven different rate constnats. The evaluation of the different rate constants is dif cult from both the viewpoints of chemical analysis of the mono-, di-, and trimethylolphenols and the mathematical analysis [Katz and Zwei, 1978] of the kinetic data.

vb.net ocr read text from pdf

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Parts Open It Up! Circuit at First Glance Step-by-Step Bending Choosing a Cool Control Layout Case Considerations Marking the Board Drilling Holes Painting Control Mounting Soldering Reassembly Testing Musicality Special Section: Casio DH 100 Squeal Repair Session and Crystal-Swapping The Squeal Fix Crystal Swapping Tweaking the Breath Control 327 327 328 328 329 329 329 329 330 330 330 331 331 331 331 332 333 334.

2-174

Not only are the different ring positions on phenol of different reactivity, but one expects that the two functional groups of formaldehyde would also differ. The second functional group of formaldehyde actually corresponds to the methylol group, since the reaction of a methylolphenol with a phenol molecule (or with a second methylolphenol) probably proceeds by a sequence such as

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vb.net ocr read text from pdf

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vb.net ocr read text from pdf

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The German denunciation of the Treaty of Versailles in 1934, the Italian-Ethiopian conflict of 1935 1936, the Spanish Civil War of 1936 1939, the reoccupation of the Rhineland in 1936, and the fear of a new world war wrought havoc with international trade, budgets, and economic readjustment During these years English trade revived, but prosperity and stability did not return A very large part of the gold reserves of the world fled to the United States World War II, 1939 1945, was the first to deserve the name total war Budgetary expenditures of belligerent states for war materials have.

2-175

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Direct kinetic measurements are not available to show the reactivity of the methylol group in this reaction compared to the initial reaction of formaldehyde. However, the general observation that the amounts of di- and polynuclear compounds present in resole prepolymers differ widely depending on the reaction condition (temperature, pH, speci c catalyst used, concentrations of reactants) indicates that the two functional groups of formaldehyde differ in reactivity. A further complication in the phenol-formaldehyde polymerization is that it may involve a decrease in functional group reactivity with molecular size. This can easily happen in systems that undergo extensive crosslinking. Such systems may cease to be homogeneous solutions before the experimentally determined gel point. The gel point may be preceded by the formation of microgel particles (Sec. 2-2d) which are too small to be visible to the naked eye [Katz and Zwei, 1978]. Functional groups in the microgel particles would be relatively unreactive because of their physical unavailability. Similar considerations would apply for the reaction period subsequent to the gel point. A decrease in reactivity with size may not be due to molecular size but a consequence of steric shielding of ortho or para positions of benzene rings within a chain compared to those positions on rings at the chain ends [Kumar et al., 1980].

already highly advanced, complex, and mature when their recorded history began. Long ages of development must have intervened between the first primitive cattle economies and the first historical societies of Mesopotamia, Egypt, Greece, and Rome. In fact, some of the characteristics and customs of the cattle economies of modern times were never known by the prehistoric ancestors of these peoples. Productive loans in kind, however, were certainly a survival. We shall now find history beginning with an elaborate effort to regulate the complex relationship between debtor and creditor.

Closing Words . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335 Appendix A: One Dozen of the Best Generic Bends . . . . . . . . . . . 339 Appendix B: Benders Resources . . . . . . . . . . . . . . . . . . . . . . 353 Appendix C: Common Electronic Components and Their Schematic Symbols. . . . . . . . . . . . . . . . . . . . . . . . 363 Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377

2-12b-2

vb.net ocr read text from pdf

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vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf

vb.net ocr read text from pdf