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The second Bank of the United States had lost its charter, and federal deposits had been transferred to state banks A period of wild speculation had ended in the collapse of 1837, which had been succeeded by a heavy depression Treasury surpluses quickly gave way to deficits From 1837 to 1841 the Treasury financed its deficits entirely through the sale of about $40 million of notes without recourse to long-term loans The idea of a new national debt for peacetime purposes met widespread political opposition; the notes were considered a temporary expedient With a change in administration in 1841 a new policy of funding notes into longer-term bonds was inaugurated The first loan, which was redeemable in only three years, was not a success and had to be broken up into two parts: 1841 $32 million 2.

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TABLE 3-13 Thermal Decomposition of Initiatorsa;b;c Initiator 2,20 -Azobisisobuyronitrile Acetyl peroxide Benzoyl peroxide Cumyl peroxide t-Butyl peroxide t-Butyl hydroperoxide

T ( C) 60 70 85 115 130 155

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All data are for decompositions in benzene solution. Data from Brandrup et al. [1999]. The units of kd are s 1 ; the units of Ed are kJ mol 1 .

4 million 51 2s of 1841, redeemable in 1845; sold at 100 = 550% 6s of 1841, redeemable in 1845; sold at 100 = 600%..

3-9a-2

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To determine the effect of temperature on the molecular weight of the polymer produced in a thermally catalyzed polymerization where transfer reactions are negligible, one must consider the ratio kp = kd kt 1=2 , since it determines the degree of polymerization (Eq. 3-98). The variation of this ratio with temperature is given by

Soon thereafter a loan was floated with the unusually long redemption term of twenty years and met with success: 1842 $8.3 million 6s of 1842, redeemable in 1863; sold from 971 2 = 6.14% to 100 = 6.00%.

3-170

Inept gestures No. We re talking about boring holes. A hand bore is a hand tool used to enlarge holes, such as the pilot holes drilled for component mounting. Bores have long, tapered, metal blades and often come in sets of two. The first will taper from about 1 8" up to 3 4". The second then takes over, tapering from 3 4" up to more than an inch. This is a must-have for general work as well as for making precise holes for mounting components larger than drill bit diameters. Be sure to have one (see Figure 5-10).

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where the energy term Ep Ed =2 Et =2 is the composite or overall activation energy for the degree of polymerization EXn . For bimolecular termination, X n is governed by Eqs. 3-98 and 3-99a and one can write

3-171

Between 1842 and 1843 a striking improvement occurred in the bond market. The Treasury took advantage of this good market to float another long-term loan at very much more satisfactory terms: 1843 $7.0 million 5s of 1843, redeemable in 1853; sold from 101 = 4.95% to 1033 4 = 4.82% current.

EX n has a value of about 60 kJ mol 1 for thermal initiator decomposition, and X n decreases rapidly with increasing temperature. EXn is about the same for a purely thermal, self-initiated polymerization (Fig. 3-16). For a pure photochemical polymerization EXn is positive by approximately 20 kJ mol 1 , since Ed is zero and X n increases moderately with temperature. For a redox polymerization, EXn is close to zero, since Ed is 40 60 kJ mol 1 , and there is almost no effect of temperature on polymer molecular weight. For all other cases, X n decreases with temperature. When chain transfer occurs in the polymerization, X n is given by an appropriate form of Eq. 3-108. The temperature dependence of X n can be quite complex depending on the relative importance of the various terms in Eq. 3-108. For the case where chain transfer to compound S is controlling (Eq. 3-119), one obtains

ln ! M 1 1 kp Ap Ep Etr;S ln ln S X n X n 0 RT ktr;S Atr;S 3-172

Not designed to warm you up (how could I resist ), the de-burrer is another hand tool I strongly suggest you get hold of. After using either a drill bit or the hand bore, you ll find that the edges of the hole are often rough. These burrs of plastic are quickly removed with a deburrer, making for cleaner control mounting and much smoother, quicker assembly. If this is a difficult tool to find where you live, you can buy a de-burring bit made for a drill press and mount it on a handle of your own design. These bits taper up very quickly from a sharp point to a width of about 1" and are also referred to as counter-sinks (see Figure 5-11).

The quantity Ep Etr;S is now EXn and can be obtained from a plot of either of the two forms of the left side of Eq. 3-172 versus 1=T. Etr;S usually exceeds Ep by 20 65 kJ mol 1 , with the more active transfer agents having lower values. The term (Ep Etr;S ) is usually 20 to 65 kJ mol 1 (Table 3-14) and the molecular weight decreases with

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