By G. E. Zaikov, B. a. Howell
This booklet is dedicated to analyzing the order and illness in polymers. figuring out those elements is critical simply because they outline diffusion houses (molecule movement pace within the polymeric matrix) and the solubility of low molecular ingredients in polymers.
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Extra info for Order And Disorder in Polymers Reactivity
Example text
It is in the agreement with proposed kinetic scheme (10). 9 kJ/mol for peroxides I and II correspondingly. Temperature dependences of rate constants 44 M. A. Тurovskyj, I. O. Оpeida, O. M. Turovskaya et al. of associates of α – oxycyclohexylhydroperoxide and α,α′ – dioxydicyclohexylperoxide with Et4N+Br– decomposition are described by equations (14) and (15) correspondingly. 1 15 2 3 4 (1/kef)·10-4, s (1/kef)·10-4, s 12 9 3 4 3 0 + 2 6 10 -1 1/[Et4N Br ], M 20 30 40 50 + -1 (1/[Et4N Br ]), M Figure 3.
Complex activation entropy is increasing, but that factor is not contradicted with well-known ideas. Changing is occurred with increasing of vibration part of active complex entropy. Rotation part of active complex entropy is changed lightly (table 2). Тable 2. Entropy and its parts (Т=363 К) № of compound 1 3 10 15 16 17 25 28 31 32 51 52 S, cal/moll/K Active complex 127,88 145,94 126,97 140,34 102,95 129,83 153,56 126,05 125,79 120,80 114,97 142,00 Initial reagent 117,22 137,11 132,86 125,04 95,52 122,5 142,21 129,31 126,25 119,43 102,87 136,87 Svib, cal/moll/K Srot, cal/moll/K Active complex 54,67 64,52 60,13 55,29 45,30 51,56 30,64 57,06 70,08 47,18 55,18 44,09 Active complex 31,40 31,52 32,13 31,14 32,07 33,28 27,30 30,97 31,30 31,13 31,13 29,71 Initial reagent 45,23 61,87 57,340 51,12 44,93 50,01 27,73 50,48 68,47 45,60 52,84 50,18 Initial reagent 30,88 31,91 32,81 31,84 32,07 34,02 27,42 30,61 31,33 31,23 32,07 30,02 Negative values of activation entropy for some acyl peroxides can be explained by increasing the interaction between valence non-combined atoms of oxygen and α-oxygen of peroxide bridge.
Ways of decomposition for some peroxides and (а) dependence between complex free energy and initial reagents free energy for those compounds (b). 2 (c). Empirical equation looks as: ∆Fc = (1,25 ± 0,08) ∆Fп р + (47,81 ± 10,88) R=0,98 SD=10,49 (6) ≠ Value ∆Η for destruction of compounds has been calculated from equation: ∆Η ≠ =Е - RT, (7) Where Т=900 К; R- universal gas constant; E-activation energy of reaction. -50 28 25 51 17 ∆F c, kcal/moll -100 1 52 10 15 -150 32 16 3 -200 -250 31 -220 -200 -180 -160 -140 -120 -100 -80 -60 ∆Fr, kc al / mol l а) Figure 2 continued on next page 26 A.