Download Liquid-Phase Reaction Rate Constants by E. T. Denisov PDF

By E. T. Denisov

The earlier 25 years in chemical kinetics have noticeable significant advances in studyiqg the mechanisms of advanced chemical re­ activities, particularly unfastened radical reactions. Many vary­ ent tools were built for quantitative stories of ordinary chemical reactions. hundreds of thousands of cost constants were measured, for hundreds and hundreds of various chemical reac­ tions. it's changing into a growing number of tough for the chemist to orient himself within the voluminous and quickly growing to be liter­ ature of chemical response kinetics. This ends up in significant bills of time in looking for, amassing. and eval­ uating quantitative kinetic info; to pointless repetition (duplication) of analysis; and to a state of affairs within which the wealthy fabric already accrued within the box of chemical kinetics is particularly usually now not absolutely used in evaluating, studying, and examining new experimental info. there's a urgent want for the construction of a sequence of handbooks on response expense constants. Such paintings was once all started a number of years in the past on the initiative of V. N. Kondrat'ev, and is now going ahead below his path on the Institute of Chemical Physics of the USSR Academy of Sciences. This publication is dedicated to liquid-phase, homolytic reactions. half One comprises information on monomolecular reactions within which molecules decompose to shape radicals, in addition to information on bi­ molecular and trimolecular reactions that shape loose radicals.

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66, the decomposipressure of the the solvent. 22. Thus, the internal pressure of the solvent can change k as much as twofold or fivefold. If only one bond is broken in the decomposition of a compound, and if the radicals that are formed do not undergo instantaneous rearrangement or decomposition, then the radicals may recombine in the solvent cage, reverting back to the original compound. In this case, one determines experimentally the apparent rate constant for consumption of the starting material, kapp = k(l - e), where k is the true constant of decomposition.

19 120-140 Paraffin oil n-C 10H22 n-C 12 H26 C 6 H5 CH(CH 3 )2 C6HSCH~H2 C 6 H6 C6 HSCI " " C 6 HSCH=CH 2 (CHS)SSi C 6 H5 (CH S )2C C 6 H5 (CH a)2C C 6 H5 (CH 3 )2C CH 3 (C 2HS ) 2C (CH S ) 2(C 2HS )C (CH 3 )2(C 2 HS )C cyc1o-Cs'i lI OH ~ 0 w 'l VI Z 0 ::! () > m ;;0 ;;0 > cr- () m 0 r- ~ 0 z (CHS)SC ------- R1 TABLE 8. \02 n-C 14 H30 " " {CH3)2CHOCH20CH2 C 4 H gOCH 2OCH 2 " " 115-129 '7,31 9O-1096,OS 80-110 5,85 11,09 32,7 7,66 25,0 lCA lCA 13,20 31,9 RlCR RlCR 80-110 5,88 14,77 3S,4 13,65 32,7 RlCR 80-110 5,90 ,ro-lIO 4,02 RlCR lS,20 31,8 RlCR [71] [71] ~[51J 12,77 S1,] CH2~H(CH2)5CH3183-203 ~,64 C eH5CH=CH 2 (CH 3 )S Si CH SOCH 2OCH 2 C 2 H5 OCH 2 OCH 2 C SH7 OCH 2OCH 2 [70J CSM 80-110 5,87 [70J CSM r [60] Ref.

In this case, one determines experimentally the apparent rate constant for consumption of the starting material, kapp = k(l - e), where k is the true constant of decomposition. For acetyl peroxide, the existence of such a form of recombination of acetyl radicals was demonstrated in [206] by means of the isotope 0 18 (for more detail on the cage effect, see Chapter III). Such a back-recombination apparently can take place for peroxides that decompose with the rupture of only one 0-0 bond, for polyphenylethanes, and for polyphenylhydrazines.

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