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app Equations 5-92 and 5-97 allow one to obtain kp , kp , and K from kp values obtained in app the absence and presence of added common ion. A plot of kp obtained in the absence of added common ion versus M 1=2 yields a straight line whose slope and intercept are app kp kp K 1=2 and kp , respectively. A plot of kp obtained in the presence of added com 1 mon ion versus [CZ] yields a straight line whose slope and intercept are kp kp K and kp , respectively. Figures 5-5 and 5-6 show these plots for polystyryl sodium in 3-methyltetrahydrofuran at 20 C. The combination of the two slopes and two intercepts allows the individual calculation of kp , kp , and K. [Note: K as well as [P ] and [P (C )] can also be independently determined from conductivity measurements.]

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5-3d-2-b Reactivity in Anionic Polymerization. Table 5-11 shows the values of K and the propagation rate constants for free ions and ion pairs in styrene polymerization in THF at 25 C with various alkali metal counterions [Bhattacharyya et al., 1965a,b]. The cor responding kp values in dioxane are also presented. The values of K and kp in dioxane could not be obtained as conductivity measurements indicated no detectable dissociation of ion pairs to free ions in dioxane. A consideration of the data in Table 5-11 allows an understanding of reactivity in anionic polymerization. The polymerization data show the much greater reactivity of the free ion compared to any of the ion pairs. The value of kp is 4 1 1 2 3 6:5 10 L mol s which is larger by a factor of 10 10 than the kp values. Similar

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Fig. 5-5 Polymerization of styrene by sodium naphthalene in 3-methyltetrahydrofuran at 20 C. After Schmitt and Schulz [1975] (by permission of Pergamon Press and Elsevier, Oxford).

differences between kp and kp have been observed in polymerizations of methyl methacrylate (MMA), 2-vinylpyridine (2VP), and isoprene (IP) [Bywater, 1985; Jeuk and Muller, 1982; Van Beylen et al., 1988]. For reference, kp has values of 3:8 103 , 1:0 105 , and 2:0 103 L mol 1 s 1 for IP (25 C), 2VP (25 C), MMA ( 98 C), respectivley, all measured in THF [Bywater, 1985].

Fig. 5-6 Polymerization of styrene by sodium naphthalene in 3-methyltetrahydrofuran at 20 C in the presence of sodium tetraphenylborate. After Schmitt and Schulz [1975] (by permission of Pergamon Press and Elsevier, Oxford).

TURN OF THE MILLENIUM, 1990 2005

TABLE 5-11 Effect of Counterion on Anionic Polymerization of Styrenea; b Polymerization in Tetrahydrofuran K 107 kp kp 9 160 2.2 > > > > 80 1.5 = 60 80 0.8 6:5 104 > > > 50 80 0.1 > ; 22 0.02

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0.94 3.4 19.8 21.5 24.5

ulatory restrictions such as those mentioned above kept the two rates far apart during most of the years from the mid-1960s to the mid-1980s In 1969, at the height of US regulatory restrictions, the CD rate averaged 199 basis points (199%) below the eurodollar rate Regulation held down US deposit rates and prevented domestic dollars from moving overseas to seek the higher returns offered by the eurodollar market Deregulation of financial markets narrowed the eurodollar-CD rate spread during the 1980s, and intermarket arbitrage virtually eliminated it during the period 1990 2004 Since banks costs of attracting dollar deposits are now the same within and outside of the United States, it presumably makes little difference to an enterprise wanting to borrow dollars whether it borrows in the United States or overseas.

Units of K are mol L 1 ; rate constants are L mol 1 s 1 . Data from Bhattacharyya et al. [1965a,b].

The K values in Table 5-11 indicate that increased solvating power affects the reaction rate primarily through an increase in the concentration of free ions When lithium is the counterion, one calculates from the equilibium constant that 15% of the propagating centers are free ions in THF (for a system where the total concentration of all propagating centers is 10 3 M) compared to zero in dioxane Since free ions are so much more reactive than ion pairs, their small concentration has a very large effect on the observed polymerization rate The majority of the propagation is carried by free ions; only about 10% of the observed reaction rate is due to ion pairs It is worth mentioning that K values independently measured by conductivity are in excellent agreement with those obtained from the kinetic measurements The K values from conductivity are 19, 15, 0.

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convert pdf to excel using javascript

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convert pdf to excel using javascript

pdf to excel javascript

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pdf to excel javascript