16CHAPTERIOn the whole, basedd onthetwo examplescited,itcanbestated that transition from the gas phase to the liquidphase has only a weakkeffect ontherateconstantforde-composition of a molecule -- at least, in certain cases
16 CHAPTER I On the whole, based on the two examples cited, it can be stated that transition from the gas phase to the liquid phase has only a weak effect on the rate constant for decomposition of a molecule - at least, in certain cases
MONOMOLECULARREACTIONS17TABLE 1.RateConstantsfor Benzoyl Peroxide Decompositionlogk0SolventElogAMethodRef.800CeHe5,6860-80[5] 16,28CSM33,35,0280-90[8]CSM14,0430,75,18[7] 50-76ICA13,4829,860-805,34[8] 13,6429,6CSMCeH,C(CHg's80-905,68CSM[8]14,4830,4.CeHsCH(CHg'25,25[9]45-80CSM13,0828,8C,H,CH=CH25,5040-70[10] 16,3033,6RICR5,3260-80RICR14,2730,8[1] 73855,56RICR14,7831,0[12]5,86CH,COCH70-95CSM[13] 14,3430,24,59[6]n-CgH1880-9014,5429,0CSMCH,COCH5, 98100-120[3] 15,18KICR31,0(CH,CO),O6,4760-80CSM[5]13,4830,7CH,CO-OCH=CH,5,0045-8013,42CSM[14] 28,3cyelo-C,H124,0380-90[6] 13,4928,2CSMcyelo-CeHiCH5,8180-90CSM14,8330,7[6]60-805,60Dioxane14,18CSM[15] 30,0CC1A59-775,45[re] 15,6832,7ICA
MONOMOlECULAR REACTIONS 17 TABLE 1. Rate Constants for Benzoyl Peroxide Decomposition Solvent 0 IlOg k 1 '0gA t E ~thO~ Ref. 80° CaHa 60-80 5,68 16,28 33,3 CSM [5] 80-90 5,02 14,04 30,7 CSM [aJ 50-,'6 5,18 13,48 29,a lCA [7] 60-80 5,34 13,64 29,6 CSM [8] C6H5C(CH3 )3 80-90 5,68 14,48 30,4 CSM [6] C6H5CH(CH3 )2 45-80 5.25 13,08 28,8 CSM [9] CaH5CH=CH 2 40-"/0 5,50 16,30 33,6 RlCR [10] 60-80 5,32 14,27 30,6 RlCR [11] 73-85 5,56 14,76 31,0 RlCR [12] C6H5COCHS 70-95 5,66 14,34 30,2 CSM [13] n-C8H18 80-90 4,59 14,54 29,0 CSM [6] CH3COCH3 100-1al 5.96 15,16 31,0 KlCR [3] (CH 3CO)20 60-80 6,47 13,49 30,7 CSM [5] CH3CO-OCH=CH 2 45-80 15,[)(l 13,42 28,3 CSM [14] cyc lo-C 6H 12 80-90 4,03 13,49 28,2 CSM [6] cyclo-C6Hn CH3 80-90 5,81 14,83 30,7 CSM [6] Dioxane 60-80 5,60 14,18 30,0 CSM [15] CC1 4 59-77 5,45 15,68 32,7 lCA [1'6]
CHAPTERI18Decomposition of Benzoyl Peroxide in VariousTABLE 2.Solvents(Temperature80°)[5,15,17]logklogkSolventSolvent5,525,955C,H,NO2C,H,OCOCH.5,525,91CHsC(CHs'sCH,COOH5,5055,875CoH,CONH,(CH,CO),O5,45CH,COOCH-CH25,805cyc1o-C,H125,445,60(CoH,CHCH,-)nC2H5I5,416Ce",CH(CH'25625Dioxane5,28CeH,CH(CHg'25,27CeH5C2H505,24CH,5,625P-CH,CH,CH3:HN65CH5,38C,H,COOH5,385,625CH,CONHCNCH,CONH,5,2855,625cyclo-C,H100CH,COCH,COOC2H55,2855,625cyclo-CeH10H,NCOOC,Hs5,32CC14CHCH25,2855,625CeHgCOOCH2CeHsC5,20CeH,NHCOOHCH25,145,57CH,CONHC,HsCeHe5,115,52(CeHs'sCHCeHeO5,52CHCC,H,CH35,09CHC5,59CoH,CHgO8,865,555CeH,CH-CHCe"sCeH,OCH,6,845CH,COCOCH.5,63CH,COOCH,CH-CH
18 CHAPTER I TABLE 2. Decomposition of Benzoyl Peroxide in Various Solvents (Temperature 800 ) [5, 15, 17] Solvent C 2H50COCHa CH 3COOH (CH 3CO)20 cyclo-C6H 12 C2H51 Dioxane 0 0 CH -C '/" I 2 )N -C6H5 CH -C 2 ~O CH 3CONH2 CH aCOCH2COOC2H5 H2NCOOC2H5 x<""'r, ~CH'// 2 C6H6 C6He CeH50CHs CH SCOOCH 2CH=CH:.! Ilogk II 5,955 5,91 5,875 5,80S 5,60 6,62S 5,625 ~,62S 5,62S ~,e25 5,626 5,57 5,52 5,52 ~,5S 5,555 ~,63 Solvent C6HSN02 C6HsC(CH a )S C6HSCONH2 CH3COIOCH~CH2 (C61-ISCHCH 2 -)n C6HSCH (CH3 )2 C6HSCH(CH3 )2 C6HSC2HS p-CHaCeH4CH3 COH5COOH CH3CONHCN cyc 10 -CeH 100 cyclo-CeH IO CCl4 C6H5COOCH2C6H6 C6H5 NHCOOH CH 3CONHC6H5 (C 6HS)3CH o CHC/ 11)0 CHC~ o CeH5CH=CHC 6H5 CHSCOCOCHS IIogk 5,52 5,52 5.50S 5,4S 5.44 5,41e 5,29 5,27 5,24 5.38 5,a6 5,285 5,286 5,32 5,285 5,20 5,14 5,11 ~.03 n.96 n,M5
19MONOMOLECULARREACTIONSTable 2(continued)logklogkSolventSolvent6,566,925CHCHCH,NO.6,546,87CH,=CH-CNm-CH,C.H,OH6,876,543,4-C12CeH,CH-CH2P-CH,CH,NO26,546,74CoH,CH,CNCeH,CH-CH26,546,63C,H,CH-CH-CH-CHC,HCeH,SsCehs6,82C,H,OCOCH-CHCOOC,HBTABLE 3.Decomposition of Symmetrically Substituted BenzoylPeroxides (CSMMethod)dioxaneacetophenoneInInInstyrene800800[15]700[13]atat[10]atSubstituent XElogklogklogk4,194,075,27P-OCH328,75,815,786,95m-OCHg28,93,334,14C-OCHg27,25,775,784,0429,9P-CHg5,67m-CH35,646,7830,24,50o-CH35,4430,2p-C(CHg'35,705,10--5,03p-iso-C,H7--5,00p-C2H5、-6,93p-C,Hs-1-5,26P-n-CgH170
MONOMOLECULAR REACTIONS 19 Table 2 (continued) Solvent Solvent \lOgk m-CHSCSH40H 6,87 CH2~CH-CN 6,S4 p-CHs Ce H4 N02 '!l,B7 S,4-CI 2C6HsCH;CH 2 6,54 C6H5CH 2CN 6,74 CsHsCH~CH2 6,S4 CSH5SSC6H5 6,SS Ce H5CH;CH-CH;CHC6Hs ~,54 C2H50COCH;CHCOOC2HS 6,62 TABLE 3. Decomposition of Symmetrically Substituted Benzoyl Peroxides (CSM Method) In acet01henone In dioxane In. styrene Substituent X at 800 13] at 800 [15] at 700 [10 logk 1 E log k log k ] p-OCHS 4.19 28,7 4.07 5,27 m-OCHS 5,81 28.9 5.76 6.95 C-OCHs ~,SS 27,2 4.14 p-CtJS 5,77 29,9 5,79 4,04 m-CHs 3,67 SO,2 5,64 ti.78 O-CH3 4,50 SO,2 5,44 p-C(CHs>s 5,70 5,10 p-iso -CsH7 5,03 p-C2Hs 5,00 P-CSHS 6,93 p-n-CBHI7o 5,26
20CHAPTERITable3(continued)InacetophenoneIndioxaneInstyrene800[15]700[10]800[13]atatatSubstituent XElogklogklogk4,08--0-0c,H6-4,080-OCH,C0Hs--16,78--P-CO,CHs-5,00o-CO,CHs---4,7029,0o-0CgHs--5,845,626,84H30,26,72P-F---6,56m-F---5,00OF---5,685,566,73p-C130,46,455,426,5830,7m-C14,595,450~C128,4-5,616,72p-Br--6,585,41m-Br--5,83-o-Br--6,79p-I---6,58m-I---7,04o-1---5,837,30p-NO230,3-7,855,5890,2m-NO2-3,197,9028,8oNo2-5,306,565,38P-CN81,25,23m-CN.--6,81p-CH,=CH---5,273,6-(NO2'2-31,2-6,893,B-(CHg'2---6,85---3,4-(OCHs'25,88---2.3-(OCHg'26,93-.2,3,4,5-C14-
20 CHAPTER I Table 3 (continued) In acetophenone In dioxane In styrene Substituent X at 800 [l3] at 800 [15] at 700 [10] logk I E logk log k o-OC2H5 4,08 o-OCH2C6H5 4,08 P~C02CH8 D,78 o-C02CH8 5,00 o-OC6H5 4,70 29,0 H B,64 80,2 5,62 U,84 p-J.' iJ,72 m-F 11,56 o-·F 5,00 p-Cl 5,58 30,4 6,56 6,73 m-Cl 1J,46 80,7 8,42 6,56 o-C1 ~,59 29,4 5,45 p-Br B,51 6,72 m-Br B,41 6,58 o-Br B,98 p-I 6,78 m-I 6,56 0-1 '7,04 p-N02 5,63 80,3 '7,30 m,.N02 B,58 30,2 '7,85 o-N02 ~,13 28,8 '7,90 p-CN 5,38 31,2 8,30 tI,56 m-CN 8,23 p . CH2=CH tI,81 S,5-(N02)2 8,27 31,2 8.B-(CHa)2 U,89 a-t-(OCHa'a D,95 2,.3-(OCH3' :I 5,68 2.S,4.6-<C1 4 U,9S