RateCoefficientforreactionofCl/OHwiththealkanes,k=A*EXP(-B/T)(cm3/molecule/s)
Alkanes
AE12AE10
B(K)
Estimated%Habstraction
kE12kE10(298K) fromspecialsiteusingSAR
SiteofAttack(%),fromSAR
CH4methane
1,85
0,066
1690
1,24
0,0064±0,00096
(1,03±0,10)E-3
100
CH2O
HCHO
CH3CH3ethane
8,61
0,83
1047
100
0,257±0,038
0,59±0,08
50;50
CH3CHO
CH3CHO
10
655
~0
1,11±0,17
1,4±0,2
16;68;16
CH3C(O)CH3
CH3C(O)CH3,CH3CH2CHO
520
~0
452
~0
2,45±0,37
2,1±0,3
3,97±0,79
2,7±0,4
296
3,74±0,75
2,1±0,3
CH3CH2CH3propane
CH3CH2CH2CH3butane
CH3CH2CH2CH2CH3
pentane
(CH3)2CHCH2CH3
2-methylpropane
14
18,1
10,1
C(CH3)4 12
2,2-dimethylpropane
CH3CH2CH2CH2CH2CH3
hexane
(CH3)2CHCH2CH2CH32methylbutane
CH3CH2CH(CH3)CH2CH3
3-methylpentane
(CH3)2CHCH(CH3)2
2,3-dimethylbutane
CH3CH2(CH2)3CH2CH3
heptane
19,8
17,7
18
12,5
800
~0
0,82±0,12
1,1±0,2
394
5,28±1,06
3,3±0,5
362
351
212
430
14:36:36:14
5;27;37;27;5
11:28:22:28:11
(5,5);53;50;5
(14,14):24:34:14
(25,25,25,25)
3;20;27;27;20;3
5,25±1,31
9:23:18:18:23:9
(3,3);45;26;19;3
2,8±0,4
(11:11):19:21:27:11
5,54±1,39
2,69±0,54
4;22;48;(4);22;4
6,14±1,53
2,2±0,3
27,6
19:61:19
7;43;43;7
6,52±1,3
3,8±0,6
11:27:15:(11):27:11
(4,4);42;42;(4,4)
(13,13):24:24:(13,13)
3;16;21;21;21;16;3
8:19:(15,15,15):19:8
Observedor Expected Majorproducts(Noxpresent)
MeasuredorExpectedProducts
CH3C(O)CH2CH3,CH3CHO
CH3CHO,CH3CH2C(O)CH3,HOCH2CH2CH2CH=O
(C2H5)2C(O),C2H5C(O)H,CH3CHO,HOCH2CH2C(O)CH2CH3
HOCH2CH2CH2C(O)CH3,C2H5C(O)C2H5,CH3CHO,CH3CH2CHO
CH3C(O)CH3,CH3C(O)H
CH3C(O)CH3,CH3CHO,CH2O
CH3C(O)CH3,CH2O
CH3C(O)CH3,HCHO
C2H5C(O)C3H7,C2H5C(O)H,C6-hydroxycarbonyls
C6-hydroxycarbonyls,hexanones
CH3C(O)CH3,C2H5C(O)H
CH3C(OH)(CH3)CH2CH2CHO,CH3C(O)CH3,CH3CH3CHO,
CH3C(O)CH2CH(CH3)CH2OH
C2H5C(O)CH3,CH3C(O)H
CH3CHO,CH3CH2C(O)CH3,CH3C(O)CH(CH3)CH2CH2OH
CH3C(O)CH3
CH3C(O)CH3,HOCH2CH(CH3)CH(CH3)CHO
C7-hydroxycarbonyls,3-et4-heptanone, C3H7C(O)H,C2H5C(O)H
C7-hydroxycarbonyls,heptanones
(CH3)3CCH(CH3)2
2,2,3-trimethylbutane
(CH3)2CHCH2CH(CH3)2
2,4-dimethylpentane
27
CH3CH2(CH2)4CH2CH3
octane
34,3
2,2,3,3tetramethylbutane
12
460
441
750
(CH3)3CCH2CH(CH3)2
2,2,4-trimethylpentane
(15,15,15):27:(15,15)
5,76±2,31
(3,3);32;24;32;(3,3)
2,77±0,55
(10,10):19:21:19:(10:10)
7,81±1,56
4,4±0,7
0,97±0,19
1,69±0,34
2;13;(17,17,17,17);13;2
3,34±0,84
2,5±0,4
9,75±1,95
CH3CH2(CH2)5CH2CH3
nonane
CH3CH2(CH2)6CH2CH3
decane
(7,7,7);67;(7,7)
3,81±0,95
1,93±0,39
7:17:(13*4):17:7
(17*3);(17*3)
(17*3):(17*3)
(4,4,4);34;44;(4,4)
CH3C(O)CH3,CH2O
CH2O,CH3C(O)CH3,C7-hydroxycarbonyls
CH3C(O)CH3,(CH3)2CHC(O)H,CH2O
CH3C(O)CH3,CH2O,CH3CHO,(CH3)2C(OH)CH2CH(CH3)CHO,
(CH3)2CHCHO
C8-hydroxycarbonyls,3-et4-octanone ,C2H5C(O)H,C3H7C(O)H
C8-hydroxycarbonyls,octanones
CH2O;CH3C(O)CH3
CH2O,CH3C(O)CH3
(11*3):23:21:(11*2)
2;11;(15*5);11;2
CH3C(O)CH3,CH2O
CH3C(O)CH3,CH2O,(CH3)2CHCHO,CH3CHO
3-,4-et5-nonanones,hydroxyketones ,CnH2n+1C(O)H;n=2-6
4,6±0,9
6:15:(12*5):15:6
C9-hydroxycarbonyls,nonanones
11±2,2
5,27±1,1
2;10;(13*6);10;2
3-,4-et5-decanones,hydroxyketones,CnH2n+1C(O)H;n=2-7
C10-hydroxycarbonyls,decanones
5:13:(11*6):13:5
réactivitéegaledes3sites
cyclopropane
6
1,4
1300
2,074
0,076±0,023
(1,4±0,4)E-3
cyclobutane
11,1
1,8
510
-56
2±0,5
2,2±0,7
réactivitéegaledes4sites
HOCH2CH2CHO,CO2
CO2,HOCH2CH2CHO
22
450
~0
4,9±1
2,9±0,6
réactivitéegaledes5sites
HOCH2CH2CH2CHO,CO2
HOCH2CH2CH2CHO,CO
30
440
6,85±1,37
3,3±0,5
réactivitéegaledes6sites
OCHCH2CH2CH(OH),CH2CHO,cyclo-hexanone
cyclohexanone,HC(O)(CH2)2CH(OH)CH2CHO
9,64±2,89
a25;b15;c2
3,75±0,75
(16*5):12:8
CH3C(O)CH2CH(OH)CH2CHO?,methylcyclo-hexanones?
CH3C(O)(CH2)2CH(OH)CH2CHO,autres,C7-hydroxydicarbonyls,
methylcyclohexanones
18,6±4,6
4,66±0,93
a18;b8
cyclopentane
cyclohexane
methylcyclohexane
cis-bicyclo[4.4.0]decane
(cis-decalin)
OCHCH2CHO?, CO,CO2,oxirane,C2H4
HCOCH2CHO,C2H4?
?
RecommendationsarethoseofCalvertetal.2008,wheredetailedkineticinformationisreviewedandevaluated
CH(CH3)3
(CH3)2CH(CH2)2CH2CH3
~0
1,4±0,1
43:(19,19,19)
CH3C(O)CH3,HCHO
3,38±0,68
(9,9):16:(18:18):22:9
CH3C(O)CH2CH2C(OH)(CH3)2,CH3CHO,CH2O,CH3C(O)CH3,
CH3C(O)CH2CH2OH,C3H7CHO,C2H5C(O)CH2CH(CH3)CH2OH,
CH3C(O)CH2CH2C(OH)(CH3)2,HOCH2CH2CH2CHO
RateCoefficientforreactionofCl/OHwiththehaloalkanes,k=A*EXP(-B/T)(cm3/molecule/s)
Haloalkanes
CH3F(HFC-41)
CH2F2(HFC-32)
CHF3(HFC-23)
CH3Cl
CH2Cl2
CHCl3
CH3Br
CH2FCl(HCFC-31)
CH3CCl3
CH3CF3(HFC-143a)
CH2FCH2F(HGC-152)
CF3CHF2(HFC-125)
AE12AE10
B(K)
kE12kE10(298K)
n
Estimated%H
abstractionfromspecial
siteusingSAR
3,14E-06
788
1,98±0,3
2
100
4,9
781
3,6±0,5
2,77E-06
933
1,07±0,16
6,9
1,591
0,33±0,05
9,27E-07
1,691
0,0283±0,0056
842
3,83±0,77
18
1,081
4,8±0,7
1,97
877
10,4±2,6
5,9
850
3,4±0,9
2,86
1,011
9,62±1,92
2,14
884
1,1±0,2
2,39
1,301
3,04±0,46
13,5
1,02
4,8±0,8
2,8
1,254
4,17±0,63
6,8
1,23
1,1±(factorof2)
4,07E-06
1,064
1,02±0,15
1,09
1,43
(9±1,3)E-2
1,57E-06
1,4
0,127±0,019
2
100
277
9,96±1,49
25
1,065
7±4
0,51
1,666
0,596±0,149
(2,6±0,7)E-3
CF2O
COF2
2
100
CF2OviaCF3OorreactionswithNOorCH4
COF2
2
100
HC(O)Cl
HC(O)Cl
0
100
HC(O)Cl
HC(O)Cl
0
100
CCl2O
COCl2
0
100
CH2O,(Br)
CH2O
0
100
HC(O)F,(Cl)
HC(O)F
2
100
CCl3CHO
CCl3CHO
2
100
3,2E-4±(factorof2)
2,84E-06
HC(O)F
HC(O)F
<6E-3
7,28E-06
Observedor Expected Majorproducts(Nox
present)
MeasuredorExpectedProducts
CF3CHO
CF3CHO
2
50;50
HC(O)F
HC(O)F
0
100
COF2,COF2viareactionswithNOorCH4
COF2
RateCoefficientforreactionofCl/OHwiththealkenes/alkynes,k=A*EXP(-B/T)(cm3/molecule/s)
Alkenes/Alkyne
AE12AE11
C2H2Acetylene
CH2=CH2Ethene
CH2=CHCH3Propene
CH2=CHCH2CH31butene
B(K)
0,78±0,16
1,06
-480
5,2±1
1,96
-438
8,52±1,3
4,85
-504
A100
26,3±3,9
6,55
-467
31,4±6,2
A50;A50
10,1
-550
A85;A13;2
A82;A12;6;0
-504
51,4±10,3
1;A49;A49;1
31,4±6,3
1;A49;A49;1
-450
86,9±17,4
A90;A7;(1,1)
67±23
A82;A12;6;0;0
67,7±17
(1,1);A34;A63;1
-410
100±20
46±9
C3H7CHO,CH2O
CH3CHO,CH3C(O)CH3
CH3C(O)CH3,CH3C(O)Cl,CO2,CH2O
aA90;b4;c2
HC(O)CH2CH2CH2C(O)H
CO,HOCH(Cl)CH2CH2CHO,CH2CH(OH)CH2CH2C(O)Cl
aA88;b4;c2
43+9
25,4
CH3COCH3,CH2O
ClCH2C(O)CH2CH2CH2OH
37±7
cyclohexene
CH3CHO
CH3C(O)CH3,HC(O)Cl
38±8
cyclopentene
CH3CHO
CH3CHClC(=O)CH3,CH3CHO,CO2,CH2O
42±8
(CH3)2C=CHCH3 19,2
2-methyl-2-butene
CH3CH2CHO,CH2O
CH3CHClC(=O)CH3,CH3CHO,CO2,CH2O
33±7
CH2=CHCH2CH2CH3
1-pentene
CH2O,CH3CHO
ClCH2C(=O)CH2CH3
35±7
CH2=C(CH3)2 9,47
2-methylpropene
CH2O,HOCH2CHO
ClCH2C(=O)CH3
34±7
64±12,8
HC(O)OH,CO,HCOCHO
ClCH2CH=O
30±6
56,4±11,2
ObservedorExpectedMajorproducts
MeasuredorExpectedProducts
CO,HC(O)Cl,HC(O)CHO
23±3
-487
CH2=C(CH3)CH=CH2
isoprene
%addition(A)orH-atom
abstractionateachC-atomsite
9,5±1,4
CH3CH=CHCH3 11
cis-2-butene
CH3CH=CH3CH
trans-2-butene
kE12kE11(298K)
HC(O)CH2CH2CH2CH2C(O)H
2-chloro-cyclohexanone
A59;A4;(1);A4;A31
CH2O;CH2=CHC(O)CH3;CH2=C(CH3)CHO
ClCH2C(=O)C(CH3)=CH2,isomersofchloromethylbutenal
Itisassumed,asevidencesuggests,thatabstractionofHatomsattachedtodouble-bondedCatoms(eg.CH2=CH2)isnegligible
RateCoefficientforreactionofCl/OHwiththearomatichydrocarbon,k=A*EXP(-B/T)(cm3/molecule/s)
Aromatic
hydrocarbon
Benzene
Toluene
AE12
AE11
2,33
1,81
B(K)
193
-338
kE12kE11
(298K)
1,22±0,24
~1,5E-5
5,63±1,13
Reactionsite
MeasuredorExpected Products
additiontoring
phenol,glyoxal,carbonyls(unidentified)
C6H4(OH)(NO2)
Benzaldehyde;o-,m-andp-cresol;glyoxal;methylglyoxal;
unsatureddicarbonyls
Benzaldehyde
Biacetyl;methylglyoxal,o-tolualdehyde;dimethylphenols;
unsaturateddicarbonyls
o-Tolualdehyde
methylglyoxal;glyoxal;m-tolualdehyde;dimethylphenols; 4-oxo-2pentenal
m-Tolualdehyde
methylglyoxal;dimethyl-phenols;p-tolualdehyde;3-hexene-2,5dione;2-methylbutenedial
p-Tolualdehyde
94%additiontoring,~6%H-abstractionfromCH3group
6,0±0,6
o-Xylene
13,6
0
13,6±3,4
~90%additiontoring;~10%H-abstraction
from-CH3groups
14,5±2,2
m-Xylène
23,1
0
23,1±3,5
~94%additiontoring;~4%H-abstraction
from-CH3groups
13,2±2,0
p-Xylène
14,3
0
13,3±3,6
~93-94%additiontoring;7-8%H-abstraction
from-CH3groups
14,4±2,2
Ethylbenzene
Styrene
7,0±1,8
12,9±3,2
58±12
36±9
additiontoringlargely,probaby>6%Habstractionfrom-C2H5group
largelyadditionofHtoCH=CH2group
C6H5CH2CHO
Benzaldehyde,CH2O
C6H5C(O)CL;CH2O
RateCoefficientforreactionofCl/OHwiththealcohols,k=A*EXP(-B/T)(cm3/molecule/s)
Alcohols
CH3OHMethanol
CH3CH2OHEthanol
CH3CH2CH2OH1propanol
CH3CH(OH)CH32propanol
AE12AE11
B(K)
kE12kE11
(298K)
Estimated%H-atom
AbstractionatEachSite
2,85
345
0,90±0,13
78;22
5,5±0,6
3
-20
3,2±0,3
6
-155
10,0±1,0
6,3
30
5,70±0,85
2,7
-190
5,1±0,51
8,8±0,9
CH3CH(OH)CH2CH32butanol
2,7
-329
8,14±1,22
6,1
-179
11,0±1,7
(CH3)2CHCH2PH2methyl-1-propanol
2,75
-371
9,55±1,43
CH3)2C(OH)CH32methyl-2-propanol
1,6
CH3CH2CH(OH)CH2C
H333-pentanol
4;91;(2);4
CH2O
CH3CHO
CH3CH2CHO;CH3CHO;CH2O
CH3C(O)CH3
5,27±0,5
5,1
2-pentanol
3;36;60;2
17,0±2,6
CH3CH2CH2CH2OH1butanol
CH3CH2CH2CH2CH2O
H1-pentanol
9;87;4
Observedor Expected Majorproducts(Noxpresent)
MeasuredorExpectedProducts
-146
8,3±1,2
CH3C(O)CH3;CH3CHO;CH2O
2;13;35;48;2
22±4
3;74;(1);21;1
1,1±0,2
(2,2);52;43;2
(30,30,30);11
C4H9CHO;C3H7CHO;CH3CHO;C2H5CHO
CH3CH2CH2CH2CHO;CH2O;CH3CH2CH2CHO;CH3CH3CHO;CH3CHO;
CH3CH(OH)CH2CH2CHO
3;59;(1);25;10;1
CH3C(O)C3H7;CH3CHO;C2H5CHO
22+6
13,0±2,0
20±5
CH3C(O)CH3;CH2O
2;12;14;30;41;1
24±4
11,0±2,2
CH3COCH3;CH2O;(CH3)2CHCHO
(CH3)2CHCH=O;CH3C(O)CH3;CH2O
3,5±0,5
11,0±1,7
CH3CH2(O)C2CH5;CH3CHO
CH3CH2C(=O)CH3CH3CHO
20,0±4,0
124
CH3CH2CH2CHO;CH3CH2CHO;CH2O;CH3CHO
CH3CH2CH2C(O)CH3;CH3CH2CHO;CH3CHO;CH2O;CH3CH(OH)CH2CHO
1;15;66;(1);15;1
CH3CH2C(O)CH2CH3;CH3CHO;CH3CH2CHO
(CH3)2CHCHCH2OH3methyl-1-butanol
1,5
(CH3)2C(OH)CH2CH3
2-methyl-2-butanol
2
-160
3,42±1,02
2,4
-331
7,3±1,8
2,5
-464
11,9±1,8
6,6
-177
12±3
CH3CH(OH)CH(CH3)2
3-methyl-2-butanol
-664
13,0±3,3
1,45
-554
9,3±1,9
5,2
-195
10,0±2,5
13,0±2,0
13,0±3,9
5,7
-650
HOCH2CH=CHCH32buten-1-ol
7,4
-734
87±17
97±24
266
36,7±9,2
3,8
-797
55±8
166±56
530
31,6±12,6
2;59;(1);35;(1,1)
59±9
2;10;12;12;26;36;1
-716
90±13
0
(24,5±9,8)
160±40
0
(44,9+18,0)
C5H11CHO;C4H9CHO;CH2O
CH3(CH2)4CHO;smalleraldehydes;varioushydrocarbonylsanddihydroxycarbonyls
(3,3);81;(2)(6,6)
CH3C(O)CH3
CH3C(O)CH3;CH2O;CH3CHO;(CH3)2CHC(O)CH3
1;9;11;11;11;22;32;1
1;8;10;10;10;10;21;29;1
0.3;7;A92
C6H13CHO;C5H11CHO;CH2O;hydroxycarbonyls
CH3(CH2)5CHO;smalleraldehydes;varioushydroxycarbonylsand
dihydroxycarbonyls
C7H15CHO;C6H13CHO;CH2O,hydroxycarbonyls
CH3(CH2)6CHO;smalleraldehydes;varioushydroxycarbonylsand
dihydroxycarbonyls
CH2O;HOCH2CHO
CH2;ClCH2CHO;CH2=CHCHO
0.1;3;A94;2
HOCH2CHO;CH2O;CH3CHO
CH3CHClCHO;CH2O;HOCH2CHClC(O)CH3;CH3CHO;CO2;CH3CH=CHCHO
0.4;7;12;A80
CH2O;HOCH2CH2CHO;HOCH2CHO
HOCH2CH2C(O)CH2Cl;ClCH2CHO;CH2O;HOCH2CH2;CH2=CHCH2CHO
0.3;14;(0.2);A85
30,0+10,5
8,1
iso-C3H7C(O)CH3;CH3C(O)CH3;CH3CHO
(CH3)2CHC(O)CH3;CH3C(O)CH3;CH3CHO
28,5±8,6
CH3CH(OH)CH=CH23buten-2-ol
HOCH2C=C(CH3)23methyl-2-buten-1-ol
50±8
CH3C(O)CH3;CH3CHO;CH3C(O)C2H5
CH3C(O)CH3;CH3CHO
42+13
HOCH2CH=CH22propen-1-ol
HOCH2C(CH3)=CH22methyl-2-propen-1-ol
(12,12);(4);68;5
37,7
CH3CH2CH2CH2CH2C
H2CH2CH2OH1octanol
iso-C4H9CHO;iso-C3H7CHO;CH3C(O)CH3;CH2O
(CH3)2CHCH2CHO;CH2O;CH3C(O)CH3
31±8
CH3CH2CH2CH2CH2C
H2CH2OH1-heptanol
HOCH2CH2CH=CH23buten-1-ol
(2,2);24;30;41;(1)
25±5
CH3CH2CH2CH2CH2C
H2OH1-hexanol
(CH3)2CHC(OH)(CH3)
22,3-dimethyl-2butanol
13,9±2,1
CH2O;CH3CHO;HOCH2CHO;CH3CH(OH)CHO
CH3CHO;ClCH2CHO;CH2=CHC(O)CH3
0.2;5;(1);A94
CH2O;HOCH2C(O)CH3
CH3C(O)CH2Cl;CH2O;CH2=C(CH3)CHO
0.1;2;A97;(0.5,0.5)
CH3C(O)CH3;HOCH2CHO
CH3C(O)CH3;HC(O)Cl;CH2O;(CH3)2C=CHCH2OH
(CH3)2C(OH)CH=CH2
2-methyl-3-buten-2ol
8,1
HOCH2CH2C(CH3)=C
H23-methyl-3-buten1-ol
6,1
-610
(4,4);(0.3);A91
30,1±9,0
-814
94±14
74±15
0.2;7;5;(1);A87
117±18
A78;16;(0.3);6;0.3
-1,229
28±6
0.1;4;A95;1;0.1
CHF2CH2OH2,2difluoro-1-ethanol
CF3CH2OH2,2,2trifluoro-1-ethanol
CxF2x+1CH2CH2OH,
x=1,4,6,8
CxF2x+1CH2OH,
x=2,3,4,6
CH2ClCH2OH
CCl3CH2OH
CxF2x+1CH(OH)2
x=1,3,4
4,72
330
1,56±0,31
6,59
351
2,0±0,5
0,49±0,15
2,53
646
0,29±0,06
1,9
863
0,105±0,015
0,75
739
0,063±0,013
0,94±0,14
6,67
403
1,73±0,35
1,68
835
0,102±0,020
0,99
823
0,063±0,013
1,28±0,38
Additiontothearomaticring
~88%;H-abstractionfromOhgroup~12%
5;88;8
3;69;27
58;42
2;94;4
0,058±0,020
CFH2CHO
CF2HCHO
CF3CHO
CxF2x+1CH2CHO
CxF2x+1CH2CHO;CxF2x+1CHO;CH2O
58;42
24;66;10
57;43
0,3±0,1
0,116±0,034
cflivre
C6H4(OH)(NO2)
3,1±1,1
0,245±0,074
HOCH2CHO;CH3CH2CHO;CH2O
CH3CH2CHClHO;CH2O;HC(O)Cl;CH3CH2CHO;CH3CH2CH=CHCHO
20±4
CH2FCH2OH2-fluoro1-ethanol
HOCH2CHO;CH2O
ClCH2CHO;CH3CH2CHO
35,0±12,3
0,45
CH2O;HOCH2CH2C(O)CH3;HOCH2C(O)CH3;HOCH2CHO
CH3C(O)CH2Cl;HOCH2CHO;CH2=C(CH3)CH2CHO;CH2O
27,4+9,6
HOCH2CH=CHcH2CH3
z-penten-1-ol
CH3C(O)CH3;CH2O;HOCH2CHO;(CH3)2C(OH)CHO
CH3C(O)CH3;ClCH2CHO
42,7±14,9
CH2=CHCH(OH)CH2C
H31-pent-3-ol
phenol
63±13
ReactionmostlyatCHgroup
CxF2x+1CHO
CH2ClCHO
CCl3CHO
CxF2x+1C(O)OH
2-methyl-3-buten-1-ol
36,3±12,7
CH2O;CH3CHO;ClCH2CHO;CH2=CHCH2CHO
4-penten-2-ol
37,5±13,1
ClCH2CHO;CH2O;CH3CHO;ClCH2C(O)CH2CH(OH)CH3;CH2=CHCH2C(O)CH3
HOOH
1,1
980
0,041±0,012
CH3OOH
5,9±1,2
CH2O
CH3CH2OOH
11,0±2,2
CH3CHO
RateCoefficientforreactionofCl/OHwiththeethers,k=A*EXP(-B/T)(cm3/molecule/s)
Ethers
CH3OCH3dimethyl
ether
CH3OCH2CH3methyl
ethylether
CH3CH2OCH2CH3
diethylether
CH3OC(CH3)3
methyl-t-butylether
AE12AE11
B(K)
kE12kE11(298K)
n
5,7
18,0±2,7
222
0
2,7±0,4
18,0±2,7
6,3±3,2
~24
12,2±1,8
28,0±5,6
3,1±0,5
15,0±2,3
20±3
37±6
0
Estimated%H-atom
AbstractionatEachSite
50;50
0
12;86;2
0
1;49;49;1
0
73;(9,9,9)
0
1;5;44;44;5;1
4,62
-289
4
80
10,3
-197
(CH3)2CHOCH(CH3)2
di-isopropylether
2,97
-361
10,0±1,5
0
(0.5,0.5);49,;49;(0.5,
0.5)
CH3CH2OC(CH3)3ethylt-butylether
3,4
-280
16,6±2,5
8,7±1,7
0
2;92;(2,2,2)
CH3CH2CH2CH2OCH2C
H2CH2CH3di-n-butyl
ether
(CH3)3COC(CH3)3di-tbutylether
CH3CH2CH2CH2CH2OC
H2CH2CH2CH2CH3di-npentylether
CH3OCH2OCH3
dimethoxymethane
(CH3O)3CH
trimethoxymethane
ethyleneoxide
(oxirane)
4,5
CH3CH2CH2OCH2CH2C
H3di-n-propylether
15,0±3,0
-550
28±4
0
0,0000027
0,0000181
-879
856
33±5
53±8
4,6±0,7
14±4
6,0±2,1
16±6
0,0910,023
0,49±0,12
CH3OC(O)H,CH2O,CH3OC(O)CH3
CH3CH2OC(O)H,CH2O,CH3CH2OC(O)CH3,CH3CHO
CH3CH2OC(O)H,CH2O,CH3CH2OC(O)CH3
O=CHOC(CH3)3;CH3OC(O)CH3;CH2O
HC(O)OC(CH3)3;CH2O;CH3C(O)CH3;CH3C(O)CH3
C3H7OC(O)H;CH3CHO;C2H5CHO;C3H7OC(O)C2H5
CH3CHO;HC(O)OCH2CH2CH3;CH3C(O)OCH(CH3)2;CH2O
iso-C3H7OC(O)CH3;CH2O
CH3C(O)OCH(CH3)2;CH2O
tert-C4H9OC(O)H;CH2O;tert-C4H9OC(O)CH3;CH3CHO
1;5;6;38;38;6;5;1
C4H9OC(O)H;C2H5CHO;C3H7CHO;C4H9OC(O)C3H7
CH3CH2CHO;HC(O)O(CH2)3CH3
3,7±0,9
14±3
-429
CH3OC(O)H
CH2O;HC(O)OC(CH3)3;CH3C(O)OC(CH3)3
47±7
7,8
ObservedorExpected Majorproducts(Noxpresent)
MeasuredorExpectedProducts
(17,17,17);(17,17,17)
0
2
0.1;4;5;5;35;35;5;4;
0.1
C5H9OC(O)H;HOCH2CH2CH2CHO
11.78;11
HOCH2CH2CH2CHO;HC(O)O(CH2)4CH3
CH3OCH2OC(O)H;CH3OC(O)OCH3
CH3OCH2OCHO
(6,6,6);82
2
CH2O;CH3C(O)OC(CH3)3
a50
CH3OC(=O)OCH3;CH2O
HC(O)O(O)CH;;CO;HC(O)OH;CH2O
HC(O)OCHO;CO;HC(O)OH;CH2O
tetrahydrofuran
tetrahydropyran
1,3-dioxane
9,4
-177
~0
17,0±2,6
27±8
0
a44;b6
7,8
-136
~0
12±2
20±6
0
a41;b6
8,6
-45
10,0±1,5
0
a37;b34;c5
16,5±2,5
1,4-dioxane
1,3,5-trioxane
furan
2-methylfuran
2-ethylfuran
3-methylfuran
2,5-dimethylfuran
2-furfural
3-furfural
5-methyl-2-furfural
6,8
-159
11,5±2,3
42
15
245
302
13
-333
18,5±3,7
5,4±0,8
10,2±1,5
40±8
20±4
67±23
39±10
116±41
44±11
93±33
113±22
110±20
87±2
40±10
132±46
120±4
54±14
35±11
3,5±1,1
49±15
4,9±1,5
51±15
5,1±1,5
HC(O)OCH2CH2CHO
HC(O)OCH(OH)CH2CH2CHO
HC(O)OCH2OCHO;CH2O;HC(O)OCH(OH)OCH2CHO;
HC(O)OC(O)OCH2CH2OH;HC(O)OH;HOCH2CHO;CH2O
ethylenecarbonate;HC(O)OCH2OCHO
0
a25
0
a33
0
aA50
HC(O)OCH2CH2OCHO
HC(O)OCH2OCHO
aA60;bA39;c1
HC(O)CH=CHC(O)H
2-chloro-2(5H)-furanone
CH3C(O)CH=CHC(O)H
2-chloro-2(5H)-furanone,CH2O?
?
2-chloro-2(5H)-furanone,CH3CHO?
?
aA49;b1
2-chloro-3(5H)-furanone,CH2O?
?
aA30;b39;c1
aA59;bA38;c3;d0.2
aA51;bA33;c16
aA51;bA33;c16
aA43;bA43;c13;d0.1
5-chloro-2(5H)-furanone,CH2O?
?
unknown?
?
unknown?
?
unknown?
0,06(±factorof2)
0,046±0,014
CH2FOCH2F(HFE-152)
CH3OCF3(HFE-143a)
CF3OCHF2(HFE-125)
2,1
1,54
0,47
2,1
CH3CH2OCF3
CF3CH2OCH3
CHF2CF2OCH3
CF3CH2OCHF2
2,6
0,55
2,5
0,63
1,42
928
1,61
1,897
CHF2CHFOCF3
CF3CHFOCHF2
CF3CHFOCF3
CF3OCF2CF2H
CH3CH2OCF2CF2H
0,439
1,78
0,53
1,655
2,57
0,18±0,06
730
0
CHF2CF2CH2OCH3
CF3CF2CH2OCH3
CH3OCH(CF3)2
CF3CHFCF2OCH3
0,87
1,112
0,012±0,002
0,013±0,004
0,00041±0,00008
(1,9±0,4)E-6
0,15±0,05
0,24±0,14
0,59±0,12
2,1±1,1
0,0222±0,0044
0,024±0,010
0,011±0,003
(1,1±0,2)E-3
0,0067±0,0033
1,3E-4(±factorof2)
0,0057±0,0029
(1,1±0,4)E-4
0,0011±0,0003
5E-6(±factorof2)
0,0021±0,0004
(2,5±0,8)E-5
0,22±0,04
0,18±0,06
0,93±0,33
2,4±1,2
0,68±0,24
4,2±2,1
0,12(±factorof2)
0,86±0,43
0,021(±factorof2)
0,021±0,007
50;50
0
100
0
100
51;49
90;10
0
89;11
0
60;40
47;53
43;57
0
100
0
100
0
51;48;1
0;11;89
11;89
42;58
9;91
FC(O)OCH2F;HC(O)F
HC(O)OCF3
CF2O
CH2O;HC(O)OCF3;CH3C(O)OCF3
CF3CH2OCHO;CF2O
CF3CH2OCH=O;CH3OCH=O;COF2
HC(O)OCF2CHF2
HC(O)OCHF2;CF2O;CF3C(O)OCHF2
CF2O;FC(O)OCF3
CF3C(O)F;CF2O
CF2O;FC(O)OCHF2;HC(O)F
CF3O(O)CF;COF2
CF2O;FC(O)CF3
CF2O
CH2O;HC(O)OCF2CF2H;CH3C(O)OCF2CF2H
CHF2CF2C(O)OCH3
CHF2CF2C(O)OCH3;HC(O)OCH2CF2CHF2
CF3CF2C(O)OCH3O
CF3CF2C(O)OCH3;HC(O)OCH2CF2CF3
HC(O)OCH(CF3)2;CF3C(O)OCH3;CF2O
HC(O)OCF2CHFCF3;
CF3CH2OCH2CF3
CF3CH2OCF2CF2H
CH3OCF2CF2CF3
1,7
751
0,137±0,027
0,070±0,014
0
50;50
1
0,195
2,06
1,394
1,616
1,54
0,0093±0,0013
(8,6±2,6)E-4
0,0117±0,0023
(9,8±2,5)E-3
0,0016±0,0008
(6,3±1,9)E-6
0,0003±0,00009
(1,3±0,7)E-7
0,14±0,06
0,32±0,13
0,012±0,004
0,011±0,003
<0,001
<3E-4
0,0117±0,0023
0,0102±0,0031
0,0665±0,020
0,079±0,024
0,24±0,06
4,3±1,5
13±3
6,3±1,9
17,9±7,2
0,038±0,008
0,031±0,011
0,012±0,002
(3,2±1,3)E-4
0,015±0,003
(4,3±1,7)E-4
0,040±0,012
(2,7±0,8)E-4
0
50;50
0
100
CF3CFHCF2OCF2H
CF3OCH(CF3)2
CF3CHFCF2OCH2CH3
n,i-C4F9OCH3(HFE7100)
11
2,069
CF3CF2CF2OCHFCF3
CH3OCF2CF2CF3
n,i-C4F9OCH2CH3(HFE7200)
2,06
1,54
4,1
n
i
852
CH3OCH2CH2Cl
CH3OCH2CH2Br
CH3OCF2CHFCl
CHF2OCF2CHFCl
Enflurane
CHF2OCHClCF3
isoflurane
CF3CH2OCClF2
2,59
1,26
0,746
1,23
1,12
1,6
1,6
1,26
1,28
2,45
1,1
2,515
43;57
100
1;54;46
100
100
0
100
49;51
26;64;10
23;71;6
0
66;34
0
20;80
0
46;54
0
100
HC(O)OCH2CF3;CF2O;CF3C(O)OCH2CF3
HC(O)OCF2CF2H;COF2
HC(O)OCF2CF2H;CF2O;CF3C(O)OCF2CF2H
HC(O)OCF2CF2CF3
CF3C(O)F;COF2
CF3C(O)F;CF2O
CF3C(O)OCF3;CF2O
HC(O)OCF2CHFCF2;CH2O;CH3C(O)OCF2CHFCF3
n,i-C4F9OC(O)H
FC(O)OCF2CF2CF3;COF2;CF3CF2CF2CF2OC(O)CF3
FC(O)OCF2CF2CF3;CF2O
HC(O)OCF2CF2CF3
HC(O)OCF2CF2CF3;CH2O
CH3C(O)OCF2CF2CF2CF3;HC(O)OCF2CF2CF2CF3
CH3C(O)OCF(CF3)CF2CF3;HC(O)OCF(CF3)CF2CF3
CH3C(O)OC4F9;HC(O)OC4F9;CH2O
HC(O)CH2CH2Cl;ClCH2C(O)OCH3;HC(O)Cl;HC(O)OCH3
HC(O)OCH2CH2Br;CH3OCHO;CH3OC(O)CH2Br
HC(O)OCH2CH2Br;BrCH2C(O)OCH3;CH2O;HC(O)OCH3
HC(O)OCF2CFCl
FC(O)Cl;CF2O;COF2
unknown?
CF3C(O)OCHF2
HC(O)OCClF2;COF2;C(O)OCClF2
CF3C(O)OCClF2;HC(O)OCClF2;CF2O
CF3CHClOCH2CH3
nC3F7CF(OCH2CH3)CF(C
F3)2HFE-7500
CH3O(CF2CF2O)mCH3
m=1,2,3
n-C4F9O(CH2)3O-nC4F9
<0,30
0,30±0,12
43;40;16
HC(O)OCHClCF3;CH2O;CH3C(O)OCHClCF3
CH3C(O)OCHClCF3;HC(O)OCHClCF3;CH2O
0,022±0,008
49;51
C3H7CF[OC(O)CH3]CF(CF3)2;C3F7CF[OC(O)H]CF(CF3)2;COF2
0,23±0,06
0,027±0,007
0,037±0,011
0,13±0,05
0,14±0,05
0,23±0,08
CF3CFHCF2O(CH2)3OCF
2CFHCF3
Formateandacetateesters;CH2O
50;50
11;78;11
0.1;11;78;11;0.1
0,29±0,10
additiontodoublebond
HC(O)O(CF2CF2O)mCH3
HC(O)O(CF2CF2O)mCH3;CH2O
C4F9OCHO;C4F9OC(O)CH2CH2OC4F9
n-C4F9OCHO;n-C4F9OCH2CHO;n-C4F9OCH2C(O)CH2O-n-C4F9
CF3CFHCF2OCHO;CF3CFHCF2OC(O)CH2CH2OCF2CFHCF3
CF3CFHCF2OCHO;CF3CFHCF2OCH2CHO;
CF3CFHCF2OCH2C(=O)CH2OCF3CFHCF2
COF2;CF3OCOF;FC(O)OF
CF2O;CF3OCFO
CF3OCF=CF2
~2,8
3,0±0,9
propyleneoxide
CF3CF2OCH3
(CF3)2CHOCH2F
CH3OCH2Cl
3,0±0,9
0,011±0,004
0,011±0,003
2,8±1,0
CH3C(O)OH;CO;CH3C(O)OC(O)H
HC(O)OCF2CF3
FC(O)OCH(CF3)2
HC(O)OCH2Cl;CH3OC(O)Cl;HC(O)OCH3
CH3OCHCl2
0,099±0,025
HC(O)OCHCl2;CH3OC(O)Cl
CHCl2CH2OCH3
4,8±1,9
HC(O)OCH2Cl2;Cl2CHC(O)OCH3;HC(O)Cl;HC(O)OCH3
CH3OCH2Br
2,6±1,0
0
2,6±1,0
HC(O)OCH2Br;HC(O)OCH3
CH3OCH2I
CHF2O(CF2OCF2O)m(CF
2O)nCHF2m=0-7,n=05
CF3[OCF(CF3)CF2]m(OC
F2)nOCF3
cyclo-[(CF3)2CF]CFCF2CF2C(OCH2CH3)
(CF(CF3)2)O
0,15
-750
1,9?
HC(O)OCH2I;HC(O)CH3;HC(O)OCF2CFCl
(5,0±1,8)E-6
CF2O
<2E-6
Noreaction
0,27±0,09
formateandacetateesters;CH2O
RateCoefficientforreactionofCl/OHwiththealdehydes,k=A*EXP(-B/T)(cm3/molecule/s)
Aldehydes
AE12AE11
B(K)
kE12kE11(298K)
n
HCHO
Formaldéhyde
CH3CHO
Acetaldehyde
CH3CH2CHO
propanal
CH3CH2CH2CHO
butanal
(CH3)2CHCHO2methylpropanal
1,26E-05
8,2
5,2
8
4,8
2,8
5,97
3,8
6,7
-613
46
-322
0
-405
-453
-411
-446
-400
2
0
1;99
0
3;4;93
0
1;17;4;78
0
(5,5);7;82
8,6
-336
8,8±1,3
7,0±1,0
15,3±2,3
8,0±1,2
18,7±2,8
12,5±2,5
23,7±4,7
16,6±4,2
25,7±5,1
15,6±2,3
26,6±4,0
Estimated%HOReactionateach
site
50;50
0
0.7;5;19;4;72
5,3
-450
24,0±3,6
5,3
-494
4,28
-568
27,8±5,6
14,2±2,8
28,5±4,3
8,6
-349
27,9±5,6
CH3CH2CH2CH2CHO
pentanal
(CH3)3CCHO2,2dimethylpropanal
CH3CH2CH2CH2CH2
CHOhexanal
CH3CH2CH2CH2CH2
CH2CHOheptanal
HCOCHOglyoxal
CH3COCHO
methylglyoxal
CH2=CHCHO
acrolein(2propenal)
(3,3,3);90
0.7;5;6;18;3;68
-306
30,0±6,0
3,1
-318
1,82
-585
7,1
-333
9,0±1,8
3,6±1,4
13,0±3,9
5,0±2,0
21,7±4,3
22,3±3,3
CO
CO2,CH2O
CO2,CH3CHO
C2H5CHO;CO2
CH3CH2CHO;CO2;CO;CH3CHO;CH2O;CH3C(O)CH2CHO
CH3C(O)CH3;CO2
CO2;CH3C(O)CH3;CO;CH2O;CH3CHO
HOCH2CH2CH2CHO;CO2;CH3CH3CH3CHO
CH3CH2CH2CHO;CO2;CO;smalleraldehydes;multifonctional
species
CH3C(O)CH3;CH2O;CO2
CO2;acetone;CH2O;CO
CH3CH(OH)CH2CH2CHO;CO2;CH3CH2CH2CH2CHO
CH3(CH2)3CHO;CO2;CO;smalleraldehydes;multifonctionalspecies
29,6±11,8
11
ObservedorExpected Majorproducts(Noxpresent)
MeasuredorExpectedProducts
0;4;5;5;7;4;63
0
50;50
0
1;99
0
A35;65
C2H5C(O)C2H5;CO2;CH3CHO;CH3CH2CHO
CH3(CH2)4CHO;CO2;CO;smalleraldehydes;multifonctional
species
CO;CO2
CO;CO2;CH2O
CO2;CO;CH2O;HOCH2CHO
ClCH2CHO;CO
CH3CH=CHCHCHO
crotonaldehyde(2-
6
-533
36±7
26,5±5,3
0
0.5;A53;47
CO;CO2;CH(O)CHO;CH3CHO;CH2O
CH3CH(Cl)CHO;CO
CH2=C(CH3)CHO
methacrolein(2methyl-2-propenal)
9
-380
32±10
0
A51;(0.5);49
CO;CO2;CH2O;HOCH2C(O)CH3
CH3CH=CHCHO E-2butenal
6
CH3CH2CH2CH=CHC
HOE-2-hexenal
CH3CH2CH2CH2CH=
CHCHOE-2-heptenal
7,5
-520
9,7
-450
benzaldehyde
26,0±3,9
-533
6,8
-185
m-tolualdehyde
p-tolualdehyde
2,4dimethylbenzaldehy
de
2,5dimethylbenzaldehy
de
3,5dimethylbenzaldehy
de
HC(O)Fformyl
fluoride
0
0.5;A53;47
13,0±5,2
o-tolualdehyde
pinonaldehyde
36±7
ClCH2C(O)CH3;CO
43±13
19±8
44±13
24±10
12,6±2,0
9,9±2
18,9±2,0
18,6±5
16,8±4,0
17,1±0,7
25,5±5,0
14,1±3,0
31,2±10,0
CH3CH2CH(Cl)CHO;CO
0
0.4;3;6;A48;43
0
0.4;3;3;6;A47;41
0
a>Ab
a>c>Ab
a>c>Ab
a>c>Ab
a>c>Ab
8,7±2
a>c>Ab
9,3±3,0
a>c>Ab
9,3±2,0
42±13
23±9
<5E-3
(1,9±0,2)E-4
CH3(CH2)3CH(Cl)CHO;CO
?
C6H4(OH)(NO2);CO2
?
C6H3(OH)(NO2)(CH3);CO2
?
C6H3(OH)(NO2)(CH3);CO2
?
C6H2(OH)(NO2)(CH3);CO2
?
?
C6H2(OH)(NO2)(CH3)2;CO2
27,8±6,0
-600
C3H7CHO;CH(O)CHO;C3H7C(O)CHO;C3H7CH(OH)CHO
CH3(CH2)2CH(Cl)CHO;CO
C6H2(OH)(NO2)(CH3)2;CO2
31,5±10,0
5,6
CO;CO2;CH(O)CHO;CH3CHO;CH2O
?
C6H2(OH)(NO2)(CH3)2;CO2
0
a84;b4;c5;d0.8;e3;f2;g0.5
CH3C(O)CH3;CH2O;unidentifiedcarbonylproducts
lossbyhydrolysisincloud,rain,or
seawaterprobablydominates
HF;HC(O)OH(aqueousphase)
CO2
CxF2x+1CHO,x=1-4
CxF2x+1CHO,x=14,6
CxF2x+1CH2CHO,
x=1,4,8
CH(O)Clformyl
chloride
CH2ClC(O)H2chloroethanal
CHCl2C(O)H2,2dichloroethanal
2,2,2trichloroethanal
2,05
378
0
0,21±0,04
0,818
1,85
702
235
CHClFCHO
CFCl2CHO
CF2ClCHO
0,58±0,9
similartoCHF2CHO(photolysis
probablymajorlossmechanism
withsomeHOattackattheCHOgroup
2,8±1,4
1,8±0,3
<0,32
0,078±0,016
3,15±0,63
1,31±0,26
2,52±0,50
1,31±0,26
0,84±0,21
0,64±0,16
2,05±0,51
1,0±0,3
0,82±0,21
5,9±1,8
1,15±0,29
0,44±0,13
2-ethylhexanal
31±9
glycoaldehyde
3-methyl-butenal
CF3CH2CH2CHO
7,3±1,5
24,5±7,3
3,4±1,0
CO2;F2CO
CO2;CF2O
similartoCHF2CHO
similartoHC(O)F
similartoCHF2CHO
similartoCHF2CHO
0
CO2;CH2O;F2CO
CO2;CxF2x+1CHO;CO2;CO
CO2;(Cl)
CO
CO2;HC(O)Cl;HCl;CH2O
CO2;HC(O)Cl
CO2;HC(O)Cl
similartoCHF2CHO
similartoCHF2CHO
similartoCHF2CHO
similartoCHF2CHO
CO2;CCl2O
CO2;HC(O)F;Cl
CO2;HC(O)F
CO2;HC(O)F;Cl
CO2;C(O)FCl
CO2;F2CO;Cl
CO2;CF2O
CO2;CO;C2H5C(=O)CH2CH2CH(OH)CH3;othermultifonctionnal
species
CO2;CH2O;HCOCHO
CH3C(O)CH3;HC(O)Cl;CO
CF3CH2CHO;CO2;CO
RateCoefficientforreactionofCl/OHwiththeketones,k=A*EXP(-B/T)(cm3/molecule/s)
Ketones
CH3C(O)CH3
Acetone
CH3C(O)CH2CH32Butanone
CH3C(O)CH2CH2CH3
2-pentanone
CH3CH2C(O)CH2CH3
3-pentanone
CH3C(O)CH(CH3)23methylbutanone
CH3C(O)CH2CH2CH2
CH32-hexanone
CH3CH2C(O)CH2CH2
CH33-hexanone
CH3C(O)CH2CH(CH3
)24-methyl-2pentanone
CH3C(O)CH2CH2CH(
CH3)25-methyl-2hexanone
cyclopentanone
cyclohexanone
AE12AE11
8,8E-12*EXP(1320/T)+1,7E14*EXP(423/T)
2,6
3,35E-06
4,0±0,6
0,38
B(K)
kE12kE11(298K)
n
0,18±0,03
745
-391
0
-705
0,21±0,03
1,1±0,22
4,0±0,6
4,1±1,2
Estimated%Hatomabstractionat
rachsite
50;50
2
8;53;40
0
2;18;76;4
11,6±3,4
5
6,6
1,45
-58
-219
0,84
-654
2,0±0,6
8,0±1,2
3,0±1,2
6,2±2,4
7,5±2,3
22;28;28;22
0
7;76;(9,9)
0
1;12;65;20;2
0,794
-828
9;12;15;62;3
0
1;10;85;(2,2)
12,8±3,8
1,25
-674
12,0±4,8
CH3CHO;CH2O;CO2
CH3CHO;CH2O;CO2;CH3C(O)CH2CHO
CH3C(O)CHO;CH3CHO
CH2O;CO2;CH3CHO;CH3CH2CHO;CH3C(O)CH2C(O)CH3;
CH3C(O)CH2CH2CHO
CH3CHO;CO2;CH3C(O)C(O)CH2CH3
CH3CHO;CO2;CH3CH2C(O)CH2CHO;CH2O?
CH3C(O)CH3;CH2O;CO2
CH3C(O)CH3;CO2;CH2O;CH3CHO
HOCH2C(O)CH2CH(O)CH2CH3;H3CC(O)CHO;C2H5CHO
C2H5CHO;CH3CHO;CO2;CH3C(OH)C(O)CH2CH(O)CH3
CH3CHO;CH2O;CO2;CH3CH2C(O)CH2C(O)CH3;CH3CH2CHO
CH3C(O)CH3;CH3C(O)CHO
CH3C(O)CH3;CH2O;CO2
0
1;11;56;30;(2,2)
13±5
2,9±1,0
11±2
6,4±2,2
18±4
CH2O;CO2
CH3CH2CH2CHO;CH2O;CH3CH2CHO;CH3CHO;CH3C(O)CH2C(O)CH2CH3;
CH3C(O)CH2CHO;CO2;CH3C(O)CH2CH2C(O)CH3
20±3
6,4±2,6
14,7±2,2
12,8±2,6
ObservedorExpected Majorproducts(Noxpresent)
MeasuredorExpectedProducts
CH3C(O)CH3;CH3C(O)CH2CHO;CH3C(O)CHO;HC(O)CH(CH3)2
CH3C(O)CH3;CH3C(O)CH2CHO
a19;b31
a15;b24
CHOCH2C(O)CH2CHO
HC(O)CH2C(O)CH2CHO;othermultifoctionalspecies?
CHOCH2C(O)CH2CH2CHO
C6cyclicdicarbonyls;acyclicmultifunctionalspecies
HOCH2C(O)CH3
hydroxyacetone
1,5
-305
4,2±1,7
5,4±2,2
0
5;91;4
CH3C(O)C(O)CH323-butanedione
CH3C(O)CH=CH2
methylvinylketone
(3-buten-2-one)
CH2=CHC(O)CH2CH3
ethylvinylketone(1penten-3-one)
CH3C(O)CH=CH2CH3
3-penten-2-one
CH3CH2C(O)CH=CH2
CH34-hexen-3-one
CH3C(O)CH2CH2CH=
CH25-hexen-2-one
1,065
450
0
50;50
2,6
-612
0,235±0,070
0,045±0,009
20,3±3,0
0
0.4;A99
20±3
25,0±10,0
CH2FC(O)CH31fluoro-2-propanone
CF3C(O)CH31,1,1trifluoroacetone
CH2ClC(O)CH3
chloroacetone
CHCl2C(O)CH31,1dichloroacetone
CCl3C(O)CH31,1,1trichloroacetone
1,3-dichloroacetone
0,055±0,011
CH2=C=Oketene
28±7
0
CH2O;CO;CO2
CH3C(O)CHO;CH2O;HC(O)CH2OH;CO2
CH2O;CO2;ClCH2CHO
A97;3;1
29±12
60±24
25±8
90±21
30±9
52±13
31±9
14,0±4,9
28±7
0,215±0,053
0,083±0,021
(1,1±0,6)E-3
0,00092±0,00023
0,438±0,110
0,19±0,05
0,402±0,100
0,018±0,005
0,0154±0,0039
0,0020±0,0005
CH3C(O)CHO
C2H5C(O)CHO;CH2O
CH3CHO;CO2;ClCH2CHO
0.2;A99;0.2
3;3;14;A80
noestimate
39;51
100
72;28
68;32
100
CH3C(O)CHO;CH3CHO
CH3CHClCHO;CO2;CH2O;CH3CHO;HC(O)Cl
CH3CHClCHO;CO2;CH3CHO;HC(O)Cl
CH2O;CH3C(O)CH2CH2CHO
ClCH2CHO;CH3C(O)CH2CHO;CH3C(O)CH2CH2C(O)CH2Cl
CO2;CH2O?
HC(O)Cl
HCOF;CO2
HC(O)F;CO2;CH2O
COF2;CO2
CF2O;CO2;CH2O
HC(O)Cl;CO2;CH2O;HCl;CO
CH2O;CO2;HC(O)Cl
HC(O)Cl;Cl;CO2;CH2O
CH2O;CO2;HC(O)Cl
COCl2;Cl;CH2O;CO2
CCl2O;CO2;CH2O
HC(O)Cl;CO2
RateCoefficientforreactionofCl/OHwiththeorganicacids,k=A*EXP(-B/T)(cm3/molecule/s)
OrganicAcids
HC(O)OHFormicacid
AE13
B(K)
kE13kE13(298K)
3,66
-50
4,3±0,9
Estimated%Habstractionfromspecial
site;Preceding"A"indicatesAdditionto
C=Cbond
Experimentalevidenceshowsreactionat
theC(O)O-Hsiteisfavored
ObservedorPredictedmajorproductorfor
Nox-containingatmosphere
H2O;CO2
1,9±0,3
CH3C(O)OHAceticacid
0,53
-767
~0
CF3C(O)OH
Trifluoroacetic
~0
Formicaceticanhydride
Formicpropanoic
anhydride
42;58
H2O;CH2O;CO2;HOCH2C(O)OH(minor)
14;73;12
CH3CHO;CH3C(O)C(O)OH;CO2
100
dryandwetdepositionlargely;CO2;COF2
A98;2
CH3C(O)C(O)OH;CH2O;CO2
0,027±0,05
CH3CH2C(O)OH
Propanoicacid
CH2=CHC(O)OHAcrylic
acid
7,0±1,4
12±3
47±14
1,24±0,62
<E-4
170(±factorof2)
2,700±740
1,0±0,3
29±9
RateCoefficientforreactionofCl/OHwiththeesters,k=A*EXP(-B/T)(cm3/molecule/s)
Esters
AE18
B(K)
kE12(298K)
n
CH3OC(O)HMethyl
formate
CH3CH2OC(O)H
Ethylformate
CH3CH2CH2OC(O)H
n-propylformate
(CH3)2CHOC(O)H
isopropylformate
CH3CH2CH2CH2OC(
O)Hn-butyl
formate
(CH3)3COC(O)Htbutylformate
CH3OC(O)CH3
methylacetate
1,28
-136
2
0,9
-713
2
20;69;11
2,41
-643
0,179±0,053
1,40±0,35
0,875±0,219
9,9±2,0
1,85±0,46
46±12
2,29±0,46
17,6±6,2
3,68±0,74
Estimated%H-atom
abstractionateachsite
47;52
2
8;55;33;4
CH3CH2OC(O)CH3
ethylacetate
4,95
-633
(11,11);73;6
2
5;33;40;20;3
0,782±0,195
14,5±5,1
0,346±0,069
2,31±0,69
1,67±0,25
1,54±0,22
17,8±3,6
2
(27,27,27);18
2
69±32
0
9;85;6
3,45±0,86
2
5;45;47;3
3,79±0,76
22,9±6,9
5,66±1,13
149±37
2
(5,5);88;3
2
4;25;30;39;2
6,47±0,97
104±21
2
(4,4);51;39;2
116±29
5,41
-145
0,669
-525
1,69E+05
-683
CH3CH2CH2CH2OC(
O)CH3n-propyl
acetate
1,46
-978
(CH3)2CHOC(O)CH3
isopropylacetate
CH3CH2CH2CH2OC(
O)CH3n-butyl
0,455
-1,353
3,03
-908
(CH3)2CHCH2OC(O)
CH3isobutyl
1,5
-1,157
72,5±18,1
ObservedorPredictedmajorproductorforNox-containingatmosphere
ExpectedorMeasuredProducts
HC(O)OH;HC(O)O(O)CH;CO2;CH2O
CO2;CH2O;HC(O)OH;CO;HC(O)OCHO
HC(O)O(O)CH;CH3C(O)O(O)CH;HC(O)OH;CH3CHO;CH2O;CO2
HC(O)OH;CO2;CH2O;HC(O)OC(O)CH3
CO2;C2H5CHO;C2H2OC(O)H;CH3C(O)CH2OC(O)H
HC(O)OH;CO2;CH3CHO;HC(O)OC(O)CH2CH3;HC(O)OCH2C(O)CH3
HC(O)OC(O)CH3;CH3C(O)CH3;HC(O)OH;CO2
HC(O)OC(O)CH3;CH3C(O)CH3;HC(O)OH;CO2;CH2O
CH3CH2C(O)CH2OC(O)H;C3H7C(O)OCHO;HC(O)OH;CH3C(O)CH2CH2CHOC(O)H
HC(O)OH;CO2;CH3CH2CHO;CH3CH2CH2CHO;HC(O)OC(O)CH2CH2CH3;
HC(O)OCH2C(O)CH2CH3;otheroxo-esters
CH(O)C(CH3)2OCHO;CO2;CH3C(O)CH3
CO2;CH3C(O)CH3;CH2O
CH3C(O)OH;CH3C(O)OC(O)H;CO;CH3C(O)O(O)CH
CH3C(O)OH;CO;CH3C(O)OC(O)H
CH3C(O)OH;CH2O;CH3C(O)OCH2CHO;HC(O)CH2OC(O)CH3
CH3C(O)OH;CO2;CH2O;CH3C(O)OC(O)CH3
HC(O)O(O)CCH3;CH3CHO;CH3C(OàOCH2CHO;CH3C(O)OH;
CH3C(O)OCH2CH2CHO
CO2;CH3C(O)OH;CH3CHO;CH2O;HC(O)OC(O)CH3;CH3C(O)OC(O)CH2CH3;
CH3C(O)OCH2CHO;oxo-esters
CH3C(O)CH3;CH3C(O)OH;CH3(O)O(O)CCH3
CH2O;CH3C(O)OC(O)CH3;CH3C(O)CH3;CO2
CH3CH2C(O)CH2OC(O)CH3;C3H7C(O)O(O)CCH3
CH3C(O)OH;CO2;CH3CH2CHO;smallaldehydes;multifunctionalspecies
CH3C(O)CH3;CH3C(O)O(O)CH;CH3C(O)OCH2C(O)H
CH3C(O)CH3;HC(O)OC(O)CH3;CH3C(O)OCH2CHO;CH3C(O)OH
CH3CH2CH(CH3)OC(
O)CH3sec-butyl
1,07
-1,24
6,1±1,2
88±18
2
3;21;71;(3);2
C2H5C(O)O(O)CCH3;C2H5C(O)CH3
CH3C(O)OC(O)CH3;CH3CHO;CH3C(O)OH;CO2;CH2O
(CH3)3COC(O)CH3tbutylacetate
3,19
-211
2
(28,28,28);17
2
-475
0,575±0,144
15,8±4,7
0,874±0,175
2
20;64;20
CH3C(O)O(O)CCH3;CH3C(O)CH3
CH3C(O)OC(O)CH3;CH3C(O)CH3;CH2O
C2H5C(O)O(O)CH;C2H2C(O)OH;COCH3C(O)C(O)OCH3;CH3CHO
CH3CH2C(O)OC(O)H;CH3CH2C(O)OH;CH2O;CH3C(O)C(O)OCH3;CH3CHO;
HC(O)C(O)OCH3;CO
CH3C(O)O(O)CC2H5;CH3C(O)OCH2CHO
CH3CH2C(O)OC(O)CH3;CH3CH2C(O)OH;CO2;CH3CHO;CH2O;
HC(O)C(O)OCH2CH3
C2H5C(O)O(O)CC2H5;CH3C(O)CH2OC(O)C2H5
CH3CH2C(O)OC(O)CH2CH3;CO2;CH3CHO;CH3CH2C(O)OH;
CH3CH2C(O)OCH2C(O)CH3;CH3C(O)OH;CO;CH3C(O)OC(O)H;
CH3C(O)C(O)COCH2CH2CH3
n-C3H7C(O)OC(O)C2H5;CO2;n-C3H7CHO
CH3CH2C(O)OC(O)CH2CH2CH3;CO2;CH3CH2CHO;CH3CH2C(O)OH;various
multifunctionnalspeciesandsmallaldehydes
CH3CH2OC(O)O(O)CH3;CH3C(O)OCH2CHO
CH3CH2CH2C(O)OH;CO;CH3CH2CH2C(O)OC(O)H;variousmultifunctional
species;smallaldehydes
CH3C(O)O(O)C3H7;C3H7CHO;CO2;CH3CHO
CH3OC(O)CH2CH3
methylpropionate
15,3±3,1
CH32CH2OC(O)CH2
CH3ethyl
propionate
2,1±0,6
34,2±10,3
4,0±1,2
CH3CH2CH2OC(O)C
H2CH3n-propyl
propionate
CH3CH2CH2CH2OC(
O)CH2CH3n-butyl
propionate
CH3OC(O)CH2CH2C
H3methyl-nbutanoate
CH3CH2OC(O)CH2C
H2CH3ethyl-nbutanoate
7;59;27;7
4;29;46;17;4
82±33
2,98
-209
6,0±1,6
3;23;28;37;6;3
160±64
1,35
-993
3,36±0,67
2
43±13
4,5±1,6
4;37;27;35;4
100±30
CH3CH2CH2C(O)OH;CO2;CH2O;CH3CH2CH2C(O)OC(O)CH3
4,7±1,4
CH3CH2CH2OC(O)C
H2CH2CH3n-propyln-butanoate
CH3OC(O)CH2CH2C
H2CH3methyl-npentanoate
CH3OC(O)C(CH3)3
methylpivalate
8;32;53;6
3;21;33;15;25;3
C2H5CHO;CO2;C3H7C(O)O(O)CC2H5
7,3±1,9
140±42
1,88
-1,028
5,26±1,31
2
5;21;35:35;4
68±20
1,19±0,30
41±11
30;(23,23,23)
CH3CH2CH2C(O)OH;CO2;CH3CHO;CH3CH2CH2C(O)OC(O)CH2CH3;CH2O;
variousmultifunctionalspecies
CH3OC(O)CH2C(O)CH2CH3;C3H7CHO;CO2;CH2O
CH3CH2CH2CH2C(O)OH;CO;CH3CH3CH3CH3C(O)OC(O)H;various
multifunctionalspecies;smallaldehydes
HC(O)O(O)C(CH3)3;CH2O;CO2;CH3C(O)CH3;(CH3)3C(O)OH
(CH3)3CC(O)OH;CO;(CH3)3CC(O)OC(O)H;CH3C(O)CH3;CH2O;CO2
CH3OC(O)CH2CH2C
H2CH2CH3methylnhexanoate
HC(O)OCH2CH2OC(
O)Hethyleneglycol
CH3C(O)OCH2CH2O
(O)CCH3ethylene
CH2=CHOC(O)CH3
vinylacetate
CC(O)CH3allyl
acetate
CH2=CHOC(O)CH2C
H3vinylpropionate
CH3OC(O)CH=CH2
methylacrylate
CH3CH2OC(O)CH=C
H2ethylacrylate
CH3CH2CH2CH2OC(
O)CH=CH2n-butyl
CH3OC(O)C(CH3)=C
H2methyl
CH3CH2OC(O)C(CH3
)=CH2ethyl
CH3CH2CH2CH2OC(
O)C(CH3)=CH2n-
3,33
-958
2
4;16;26;26;26;3
92±28
4,77E+06
-493
2,29E+06
-731
0,484±0,121
3,2±0,8
2,16±0,54
5,7±1,4
24,9±5,0
268±91
26,6±5,3
5;45;45;5
1;49;49;1
0
A99;1
0
A91;8;0.1
130±45
2,00E+06
-556
2,50E+06
-552
3,74E+05
-1,177
2,68E+06
-811
2,44E+06
-982
methylsalicylate
CH3OC(O)CH3
dimethylcarbonate
7,36±1,84
6,31E-01
-525
24,6±2,8
206±62
12,9±2,6
187±56
15,9±3,2
218±74
19,4±6,8
272±82
40,7±8,1
254±76
43±11
271±108
65,8±13
370±74
~11
2,5±0,6
0,326±0,082
2,3±0,6
A98;1,1
0
3;A97
0
2;17;A81
0
2;11;13;13;A61
0
1;(5);A94
1;12;(5);A82
0
1;7;8;8;(4);A76
Aa96;b2;c1
2
50;50
CH3OC(O)CH2C(O)C3H7;C5H11CHO;CO2;CH2O
CH3CH2CH2CH2CH2C(O)OH;CO;CH3CH2CH2CH2CH2C(O)OC(O)H;various
multifunctionalspecies;smallaldehydes
HC(O)O(O)CH;HC(O)OH;CO
HC(O)OC(O)H;HCOOH;CO
CH3C(O)O(O)H; CH2O; CO2
CH3C(O)OC(O)H;CH3C(O)OH;CO
CH2O;HC(O)CH2OC(O)CH3
CH3C(O)OC(O)CH2Cl;CH3C(O)OH;CO2;HC(O)Cl
CH2O;HC(O)CH2OC(O)CH3
CH3C(O)OCH2C(O)CH2Cl;CH3C(O)OCH2CHO;HC(O)Cl;ClCH2CHO;
CH3C(O)OCHO;CH3C(O)OH;CO
CH2O;CH(O)OC(O)C2H5
CH3CH2C(O)OC(O)CH2Cl;CH3CH2C(O)OH;CO2;HC(O)Cl
HCOC(O)OCH3;CH2O
ClCH2C(O)C(O)OCH3
CH2O;HC(O)C(O)OC2H5
ClCH2C(O)C(O)OCH2CH3
HC(O)C(O)OC4H9;CH2O
ClCH2C(O)C(O)OCH2CH2CH2CH3
CH3C(O)C(O)OCH3;CH2O
HC(O)Cl;CH3C(O)C(O)OCH3
CH3C(O)C(O)OC2H5;CH2O
CH3C(O)C(O)OC4H9;CH2O
HC(O)Cl;CH3C(O)C(O)OCH2CH2CH2CH3
?
HC(O)OC(O)OCH3;CH2O;CO2
HC(O)OC(O)OCH3;CH2O;CO2
CF3OC(O)H
trifluoromethyl
formate
CHF2C(O)OCH3
methyl2,2CF3C(O)OCH3
methyl
trifluoroacetate
CF3C(O)OCH2CH3
ethyl
trifluoroacetate
CF3C(O)OCH2CF3
2,2,2-trifluoroethyl
trifluoroacetate
CH2=CHC(O)OCH2C
H2(CF2)3CF3(4:2
fluorotelomer
acrylate)
1,17E+06
3,23E+05
1,274
0,0163±0,0041
557
0,0098±0,0025
0,133±0,033
0,20±0,05
0,0498±0,0125
0
probablydissolution
andhydrolysisinoceans
mostsignificantfate;
100
0
100
CF2O;CO;CO2?
CH2O;CO2;COF2
0
100
CH2O;CO2;CF3OH;COF2
0,088±0,022
0,236±0,059
CO2;CF3C(O)F;HC(O)F
CF3C(O)OC(O)H;CF3C(O)OH;CO
63;37
CH3CHO;CO2;CF3OH;COF2
1,75±0,44
CF3C(O)OC(O)CH3;CF3C(O)OH;CO2;CH2O
0,094±0,024
CF3CHO;CO2;CF3OH;COF2
0,094±0,024
CF3C(O)OH;CO2;CF2O;CF3C(O)OC(O)CF3
11,5±2,3
207±41
A82;18;0.2
CH2O;CH(O)C(O)OCH2CH2C4F9
ClCH2C(O)C(O)OCH2CH2C4F9
methyl-2methylpropionate
42±13
(CH3)2CHC(O)OH;(CH3)2CHC(O)OC(O)H;CH3C(O)C(O)OCH3;CH2O
n-butyl-n-butanoate
170±51
CH3CH2CHO;n-C3H7C(O)OC(O)-n-C3H7;smalleraldehydes;various
multifunctionalspecies
methyl-2methylbutanoate
90±27
C2H5CH(CH3)C(O)OH;CO;C2H5CH(CH3)C(O)OC(O)H;variousmultifunctional
species;smalaldehydes
methylnheptanoate
methylcyclohexane
carboxylate
CH3CH=CHC(O)OCH
3methylcrotonate
ethylcrotonate
(CH3)2C=CHC(O)OC
H3methyl3,3dimethylacrylate
perfluoroethyl
formate
perfluoro-n-propyl
formate
perfluoroalkyl
formats(nCxF2x+1OC(O)H,
x=4,5,7,10)
difluoromethyl
trifluoroacetate
135±41
287±86
CH3CH2CH2CH2CH2CH2C(O)OH;CO;CH3CH2CH2CH2CH2CH2C(O)OC(O)H;
variousmultifunctionalspeies;smallaldehydes
c-C6H11C(O)OH;CO;c-C6H11C(O)OC(O)H;variousmultifunctionalspeciesfrom
ringabstraction
210±42
CH3CHCLC(O)OCH3;CH2O;CO2;HC(O)C(O)OCH3
252±76
CH3CHCLC(O)C(O)OCH2CH3;CH2O;CO2;HC(O)C(O)OCH2CH3
358±143
CH3C(O)CH3;HC(O)C(O)OCH3;ClC(O)C(O)OCH3
0,0013±0,005
CF2O;CO;CO2?
0,0091±0,0032
CF2O;CO;CO2?
0,014±0,005
CF2O;CO;CO2?
<4E-5
CF2O;CO2
RateCoefficientforreactionofCl/OHwithN-containingoxygenates,k=A*EXP(-B/T)
(cm3/molecule/s)
N-Oxygenates
AE12
B(K)
HC(O)NHCH3Nmethylformamide
kE11kE12(298K)
PositionofOHattack
ObservedorPredictedmajorproducts
8±2,8
noestimates
?
noestimates
?
noestimates
?
100
CH2O
42;58
CH3CHO
42;47;12
CH3C(O)CH2ONO2;CH3CHO;CH2O?
(45,45);10
CH3COCH3
11;72;15;3
CH3C(O)CH2CH2ONO2
6;38;47;8;2
C2H5C(O)CH2CH2ONO2
8;5;11;68;8
CH3CH(ONO2)CH2C(O)CH3
2;48;48;2
O2NOCH2C(O)CH2CH2ONO2;CH2O;CHOCH(ONO2)CH3
3;91;2;4
HCOCH(ONO2)CH3
8,6±2,6
HC(O)N(CH3)2N,Ndimethylformamide
14±4
CH3C(O)N(CH3)2N,Ndimethylacetamide
16±5
CH3ONO2Methylnitrate
CH3CH2ONO2Ethylnitrate
17±5
23±7
40
65
(CH3)2CHONO2iso-propyl
nitrate
62
CH3CHCH2CH2CH32-pentyl
nitrate
387
0,18±0,09
0,37±0,07
1,2
CH3CH2CH2CH2CH2ONO2npentylnitrate
0,023(±factorof2)
0,024±0,004
CH3CH2CH2ONO2n-propyl
nitrate
CH3CH2CH2CH2ONO2nbutylnitrate
845
168
0,58±0,17
2,2±0,4
230
0,29(±factorof2)
0,38±0,11
1,6±0,3
0,82±0,25
3,6±1,8
14,5±4,4
1,7±0,5
10,1±3,0
O2NOCH2CH2CH2CH2ONO2
1,4-dinitrooxybutane
6,3±1,9
HOCH2CH(ONO2)CH32nitrooxy-1-propanol
6,7±2,0
3,9±1,2
4,2±1,3
O2NOCH2CH(OH)CH31nitrooxy-2-propanol
5,1±1,5
HOCH2CH(ONO2)CH2CH32nitroxy-1-butanol
7,4±2,2
7;65;10;9;8
CHOCH(ONO2)CH2CH3
2;37;(3);54;4
O2NOCH2CH(CH)C(O)CH3;O2NOCH2C(O)CH2CH3
2;91;(2);5;0.5
CH3C(O)CH2CH2ONO2
3;85;10;2;0.6
CHOCH2CH(ONO2)CH3
2;54;40;3;0.6
CHOCH2CH2CH2ONO2
2;13;(3);57;22;3
C2H5CHO;O2NOCH2CHO
1;70;(1);25;2;0.4
CH3C(O)CH2CH2CH2ONO2
2;46;34;16;3;0.5
HC(O)CH2CH2CH(ONO2)CH3
1;39;29;14;2;0.5
CH(O)CH2CH2CH2CH2CH2ONO2
noestimates
photodecompositionmajorreaction
noestimates
photodecompositionmajorreaction
noestimates
photodecompositionmajorreaction
noestimates
photodecompositionmajorreaction
0,98±0,29
7,0±2,1
0,87±0,26
10,4±3,1
CH3CH(OH)CH2CH2ONO24nitroooxy-2-butanol
1,40±0,41
11,9±3,6
HOCH2CH2CH(ONO2)CH33nitroooxy-1-butanol
1,39±0,42
12,6±3,8
HOCH2CH2CH2CH2ONO24nitrooxy-1-butanol
1,82±0,55
9,8±2,9
O2NOCH2CH(OH)CH2CH2CH
31-nitrooxy-2-pentanol
1,25±0,38
32,1±9,6
CH3CH(OH)CH2CH2CH2ONO
25-nitrooxy-2-pentanol
2,05±0,62
28,6±8,6
HOCH2CH2CH2CH(ONO2)CH
34-nitrooxy-1-pentanol
1,56±0,47
30,9±9,3
HOCH2CH2CH2CH2CH2CH2O
NO26-nitrooxy-1-hexanol
CH3CH2ONOethylnitrite
O2NOCH2C(O)CH3
4,5±1,4
O2NOCH2CH(OH)CH2CH31nitrooxy--2-butanol
CH3ONOmethylnitrite
2;89;5;5
2,44±0,73
1
1,764
2,7±0,9
0,21±0,03
0,67±0,20
<2,75
CH3CH2CH2ONOn-propyl
nitrite
1,1±0,3
CH3CH2CH2CH2ONOn-butyl
nitrite
2,4±0,7
<6,04
<13
3,8±1,1
CH3CH2CH2CH2CH2ONOnpentylnitrite
CH3NO2nitromethane
noestimates
photodecompositionmajorreaction
noestimates
additiontotheN-atomsuggestedtodominateH-atom
abstraction
<23
0,58
1,102
0,014±0,0003
~7E-4
CH3CH2NO2nitroethane
1,7
0,017±0,0005
100;0
CH(O)CH2NO2?
56;44;00
CH(O)CH2CH2NO2?
11;73;15;0
CH3C(O)CH2CH2NO2?
6;40;49;4;0
C2H5C(O)CH2CH2NO2?
additiontoring
?
100
CH2O;CO2;NO2?
0,019±0,004
CH3CH2CH2NO21nitropropane
3,8
CH3CH2CH2CH2NO21nitrobutane
5,8
CH3CH2CH2CH2CH2NO21nitropentane
0,108
nitrobenzene
934
700
0,36±0,07
0,094±0,024
646
0,66±0,33
<0,001
703
1,0±0,4
0,114±0,034
0,6
440
0,14±0,04
0,0094±0,024
CH3C(O)O2NO2peroxyacetyl
nitrate
0,0185±0,0034
2-heptylnitrate
26,4±7,9
2-nitrooxy-1-pentanol
1,59±0,48
peroxypropionylnitrate
0,114±0,034
<0,001
GroupfactorsderivedbyKwokandAtkinson(1995)forestimatingk(298K)valueforHO
abstractionofHatomsfromorganiccompounds.AlsogivenareT°dependent
parametersCandDink=CT^2*EXP(-D/T)foreachgroup
Group
CE18
D,K
kE12(298K)
cm3/molecule/s
-CH3
4,49
320
0,136
-CH2-
4,5
-253
0,934
>CH-
2,12
696
1,94
Formyl-H
kabst(-OH)
kabst(-OC(O)H)
2,1
85
1,94
0,14
0,09
AllylicH-atoms (locatedoncarbonatomsthatarenexttoaC=Cgroup)
-CH3-(primary)
0,75/CH3-group
-CH2-(secondary)
2,32/CH2-group
>CH-(tertiary)
3,1/CH-group
Thevaluesinthistableandthoseintable2wereusedinthisworkinmakingtheSAR
estimatesofpercentageabstractionatvarioussitesforallgroupsofcompoundsother
thanthealkanesandhaloalkanes
SubstituentfactorsF(X)at298K(KwokandAtkinson,1995)
X
F(X)at298K
X
F(X)at
298K
X
F(X)at298K
-CH3
1
-OCF2-
0,17
-OC(=O)R
1,6
-CH2-
1,23
-OCHF2
0,17
-OC(=O)H
0,6
>CH-
1,23
-OCH2F
0,17
-C(=O)OH
0,74
>C<
-F
-Cl
1,23
0,094
0,38
-OCH2CF3
-OCH(CF3)2
-OCHClCF3
0,44
0,44
0,44
-CH2ONO2
>CCHONO2
->CONO2
0,2
0,2
0,2
-Br
-I
-CH2Cl
0,28
0,53
0,36
-C(=O)CF3
=O
-CH(=O)
0,11
8,7
0,75
-ONO2
-CN
-CH2CN
0,04
0,19
0,12
-CHCl2
0,36
>C=O
0,75
-NO2
0
-CHCl->CCl-CH2Br-CHBr-CCl3-CF3
-CHF2
-CH2F
-CHF-CF2-CF2Cl
-CFCl2
-OCF3
0,36
0,36
0,46
0,46
0,069
0,071
0,13
0,61
0,21
0,018
0,031
0,044
0,17
-CH2C(=O)>CHC(=O)
->CC(=O)-C6H5
>C=C<
-C≡C-OH
-CH2OH
>CHOH
->COH
-OR
-C(=O)Cl
-C(=O)OR
3,9
3,9
3,9
1
1
1
3,6
2,6
2,6
2,6
8,4
0,067
0,31
-CH2NO2
-NHC(O)OR
-OC(O)NHR
-NH2
-NHR
-NR2
-N(R)NO
-N(R)NO2
3-memberring
4-memberring
5-memberring
6-,7-,or8-memberring
0,14
7,5
4,8
9,3
9,3
9,3
9,3
9,3
0,02
0,28
0,64
1
ThekvaluesofgroupratecoefficienrtsforHO
abstractionofHatomsderivedfrombestfitsofthe
alkaneandhaloalkanedatabyCalvertetal.(2008)
Group
kE12(298K)
cm3/molecule/s
-CH3
0,136
-CH2-
0,78
>CH-
1,37
Thesevalueswereusedinthisworktoestimaterate
coefficientsforH-atomabstractionithealkanesand
haloalkanes
SubstituentfactorsF(X)at298KforH-atomabstractionbyHOradicalsderived
fromalkaneandhalohalkanedatafitsbyCalvertetal.(2008)
X
F(X)at298K
X
F(X)at298K
-CH3
1
-CHI
0,5
-CH2-
1,35
3-memberring
0,02
>CH-
1,35
4-memberring
0,28
>C<
-F
-Cl
1,35
0,164
0,419
5-memberring
7-memberring
8-memberring
0,64
1
1
-Br
-I
-CH2Cl
0,514
0,792
0,403
-CHCl2
0,403
-CCl3-CHCl->CCl-CH2Br-CHBr-CF3
-CHF2
-CH2F
-CHF-CF2-CF2Cl
-CFCl2
-CF2Br
-CH2I
0,086
0,403
0,403
0,4
0,4
0,052
0,106
0,106
0,216
0,045
0,11
0,045
0,15
0,5
Groupratecoefficients(298K)forestimationofratecoefficientsfortheHOradicals
additiontomultiplebondedcarbonstructuralunits(KwokandAtkinson1995).
StructuralUnit
kE12(298K)
cm3/molecule/s
CH2=CH-
26,3
CH2=C<
51,4
cis-CH=CH-
56,4
trans-CH=CH-CH=C<
>C=C<
64
86,9
110
CH2=CHCH=CHCH2=CHC(-)=CH2
CH2=CHCH=C<
105
105
142
CH2=CHC(-)=CH-
142
-CH=CHCH=CHCH2=C(-)C(-)=CH2
CH2=CHC(-)=C<
CH2=C(-)CH=C<
-CH=CHCH=C<
CH2=C(-)C(-)=CH-CH=C(-)CH=CH>C=CHCH=C<
CH2=C(-)C(-)=C<
-CH=C(-)C(-)=CH-CH=CHC(-)=C<
-CH=C(-)CH=C<
-C≡CH
-C≡C-
142
142
190
190
190
190
190
260
260
260
260
260
7
27
Thesevalueswereusedinthisworkto
estimateratecoefficientsforOHaddition
reactionsinthecyclicalkenesandthe
unsaturatedoxygenated
GroupsubstituentfactorsC(X)at298KfoHOradical
additionto>C=C<and-C≡C-bonds(Kwokand
Atkinson,1995)
Substituent
group
C(X)298K
-F
0,21
-Cl
0,21
-Br
0,26
-CH2Cl
-CH(=O)
-C(=O)CH3
0,76
0,34
0,9
-CH2ONO2
>CHONO2
-C(=O)OR
0,47
0,47
0,25
-OR
1,3
-CN
-CH2OH
0,16
1,6
ValuesoftheparametersusedinestimatingHOratecoefficientsfor
alkeneandconjugateddienecompoundsbythemethodofpeetersetal.
(2007)
Parameters
ValueE11
(cm3/molecule/s)
Monoalkenes
kprim
0,45
andnon-conjugated
ksec
3
polyalkenes
ktert
5,5
conjugated
alkenes
ksec/prim
ksec/sec
ksec/tert
3
3,7
5
ktert/prim
ktert/sec
ktert/tert
5,7
8,3
9,9
Electrophilicsubstituentconstants(∑+)foruseinestimatingtherateconstant
(298K)forHOadditiontothearomaticringincompounds(Zetzsch,1982)
Group
!+(ortho-,parapositions)
!+(meta-positions)
methyl-CH3
-0,331
-0,066
ethyl-CH2CH3
-0,295
-0,064
iso-propyl-CH(CH3)2
-0,28
-0,06
tert-butyl-C(CH3)3
phenyl-C6H5
methoxy-OCH3
-0,256
-0,179
-0,778
-0,59
0,109
0,047
phenoxy-OC6H5
hydroxy-OH
carboxy-C(=O)OH
-0,5
-0,92
0,421
0,322
carbomethoxy-C(=O)OCH3
0,489
0,368
carboethoxy-C(=O)OCH2CH3
nitro-NO2
0,482
0,79
0,366
0,674
Parametersusedinestimatingratecoefficients
forreactionofClwiththealkanesandthe
monofunctional,acyclicandsaturatedalcohols
andethers,takenfromCalvertetal.(2008)
kprim
2,84E-11
ksec
8,95E-11
ktert
6,48E-11
Substituentfactor
F(-CH3)
1
F(-CH2-;>CH-;>C<)
0,8
F(-OH)
1,18
F(-CR2OR)
1,45
0,4
Theratecoefficientforreactionata-CH3
group(kprim)isassumedtobeunaffectedby
neighboringalkylgroups
Parametersusedinestimatingratecoefficientsforreactionof
Clwithsaturated,monofunctionalcarbonylspecies
(aldehydes,ketones,acids,andesters)
k(HC(O)O-)E-11cm/molecule/s
F(=O)
F(-C(=O)R)
F(-CR2C(=O)R)
F(-C(O)OR)
F(-CR2C(=O)OR)
F(-OC(O)R)
F(-CR2OC(O)R)
K(HC(O)O-)
includingacetone
1,32
0,039
0,85
9,50E-04
0,22
0,061
0,21
0,018
excludingacetone
1,34
0,24
0,57
9,50E-04
0,22
0,061
0,21
0,018