table 1: high temperature rate data for oh + neo...

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Site-Specific Reaction Rate Constant Measurements for Various Secondary and Tertiary H-Abstraction by OH Radicals Jihad Badra, Aamir Farooq* Supplementary Material: Tables S1-S3, Figures S1-S5 Table S1: Sub-mechanism for 2,2-dimethyl-pentane. Reaction Pre- exponential Factor (A) (cm, mol, s) Temperat ure exponent (B) Activation energy (cal/mol) c7h16-2-2 + oh c7h15-2- 2a + h2o 1.578E+10 0.97 1590 c7h16-2-2 + oh c7h15-2- 2b + h2o 4.68E+07 1.61 -35 c7h16-2-2 + oh c7h15-2- 2c + h2o 4.68E+07 1.61 -35 c7h16-2-2 + oh c7h15-2- 2d + h2o 5.28E+09 0.97 1590 c7h15-2-2a ic4h8 + nc3h7 3.68E+15 -0.56 31359 c7h15-2-2a ch3 + dc6h12 9.55E+14 -0.59 30592 c7h15-2-2b ch3 + cc6h12 5.31E+13 0.11 30542 c7h15-2-2c c3h6 + ic4h9 2.64E+15 -0.55 31136 c7h15-2-2d c2h4 + neoc5h11 2.64E+15 -0.55 31136 neoc5h11 ic4h8 + ch3 8.466E+17 -1.111 32930 1 a

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Page 1: Table 1: High Temperature Rate Data for OH + neo …repository.kaust.edu.sa/.../10754/347279/2/mmc1.docx · Web viewSaudi Aramco: Company General Use Saudi Aramco: Company General

Site-Specific Reaction Rate Constant Measurements for Various Secondary and Tertiary H-Abstraction by

OH Radicals

Jihad Badra, Aamir Farooq*

Supplementary Material: Tables S1-S3, Figures S1-S5

Table S1: Sub-mechanism for 2,2-dimethyl-pentane.

ReactionPre-exponential Factor (A) (cm,

mol, s)

Temperature exponent

(B)

Activation energy

(cal/mol)

c7h16-2-2 + oh c7h15-2-2a + h2o 1.578E+10 0.97 1590c7h16-2-2 + oh c7h15-2-2b + h2o 4.68E+07 1.61 -35c7h16-2-2 + oh c7h15-2-2c + h2o 4.68E+07 1.61 -35c7h16-2-2 + oh c7h15-2-2d + h2o 5.28E+09 0.97 1590c7h15-2-2a ic4h8 + nc3h7 3.68E+15 -0.56 31359c7h15-2-2a ch3 + dc6h12 9.55E+14 -0.59 30592c7h15-2-2b ch3 + cc6h12 5.31E+13 0.11 30542c7h15-2-2c c3h6 + ic4h9 2.64E+15 -0.55 31136c7h15-2-2d c2h4 + neoc5h11 2.64E+15 -0.55 31136neoc5h11 ic4h8 + ch3 8.466E+17 -1.111 32930

1

a

b

cd

a

a

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Table S2: Sub-mechanism for 2,4-dimethyl-pentane.

ReactionPre-exponential Factor (A) (cm,

mol, s)

Temperature exponent (B)

Activation energy

(cal/mol)

c7h16-2-4 + oh c7h15-2-4a + h2o 2.112E+10 0.97 1590c7h16-2-4 + oh c7h15-2-4b + h2o 1.146E+11 0.51 63c7h16-2-4 + oh c7h15-2-4c + h2o 4.68E+7 1.61 -35c7h15-2-4a ic4h9 + c3h6 3.68E+15 -0.56 31359c7h15-2-4a ch3 + dc6h12 9.55E+14 -0.59 30592c7h15-2-4b c3h7 + ic4h8 1.71E+12 0.31 26610c7h15-2-4c ch3 + cc6h12 9.55E+14 -0.59 30592

2

ab

b

a

a

c

a

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Table S3: Sub-mechanism for 2,2,4,4-tetramethyl-pentane.

Reaction

Pre-exponential Factor (A)

(cm, mol, s)

Temperature exponent

(B)

Activation energy

(cal/mol)

c9h20-2-2-4-4 + oh c9h19-2-2-4-4a + h2o 3.168E+10 0.97 1590c9h20-2-2-4-4 + oh c9h19-2-2-4-4b + h2o 4.68E+7 1.61 -35c9h19-2-2-4-4a ic4h8 + neoc5h11 3.68E+15 -0.56 31359neoc5h11 ic4h8 + ch3 8.466E+17 -1.111 32930c9h19-2-2-4-4a ch3 + c8h16-1-2 9.55E+14 -0.59 30592c9h19-2-2-4-4b ch3 + c8h16-2-2 1.90E+15 -0.59 30592

3

a

ba

a

a

aa

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Fig. S1. Effect of methyl branching on OH + alkane rate constants at low temperatures

The experimental data of 2-methyl-butane + OH is taken from: Atkinson et al.1, Cox et al.2, Darnall et al.3 and Lloyd et al.4.The experimental data of 2,2-dimethyl-propane + OH is taken from: Greiner5, Darnall et al.3, Paraskevopoulos and Nip6, Atkinson et al.7, Tully et al.8 and Nielsen et al.9.The experimental data of 2,3-dimethyl-butane + OH is taken from: Wilson et al.10, Atkinson et al.7, Darnall et al.3 and Darnall et al.11.The experimental data of 2,2-dimethyl-butane + OH is taken from: Atkinson et al.1 and Harris and Kerr12.

4

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Fig. S2. Comparison of the rate constants of iso-octane + OH and 2,2,3,3-tetramethyl-

butane + OH.

The experimental data of iso-octane + OH is taken from: the current work, Bott and Cohen13, Greiner5 and Atkinson et al.1.The experimental data of 2,2,3,3-tetramethyl-butane + OH is taken from: Bott and Cohen13, Greiner5, Tully et al.8, Atkinson et al.1 and Baldwin et al.14.

5

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Fig. S3. Comparison of the rate constants of n-hexane + OH and 3-methyl-pentane + OH.

n-hexane experimental data is taken from: Badra et al.15, Koffend and Cohen16, DeMore and Bayes17, Donahue and Anderson18, Campbell et al.19 and Atkinson et al.1. 3-methyl-pentane experimental data is taken from: Badra et al.15, Lloyd et al.4 and Atkinson et al.1.

6

Page 7: Table 1: High Temperature Rate Data for OH + neo …repository.kaust.edu.sa/.../10754/347279/2/mmc1.docx · Web viewSaudi Aramco: Company General Use Saudi Aramco: Company General

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P3

P3

P3

S31S10

P1

P2

P2

P2

P2

S22

T100

T100

P3

P3

P3

P2

P2

S32

T100P3

P3

P3

P3

P3

P3

S33

P1

P1

S10

S10

S11

S11

P2

P2

T100

S21

S10

P1

n-Hexane 2-Methyl-Pentane

2-2-4-Trimethyl-Pentane (Iso-Octane)

2,2,4,4-Tetramethyl-Pentane

2,2-Dimethyl-Pentane 2,4-Dimethyl-Pentane

3-Methyl-Pentane

P1

P1

P2

S20 S20

T101

2,2-Dimethyl-Butane

P3

P3

P3S30

P1

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Fig. S4. Schematics showing the molecular structures of the eleven studied alkanes with the locations of the site-specific rate constants. Black means it is available from literature,

Red indicates it is derived in the current work.

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2,2-Dimethyl-Butane

P2

P2

P2

P2T200

T200

P2

P2

T100

S21S11’

S11S10

P1

2-Methyl-Heptane

4-Methyl-Heptane

P1P1

P2

S10S10S21 S21

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Fig. S5. Arrhenius plot of the secondary site-specific rate constants for a temperature

range of 250 – 1450 K.

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References

1. Atkinson, R.; Carter, W. P. L.; Aschmann, S. M.; Winer, A. M.; Pitts, J. N., Kinetics of the reaction of oh radicals with a series of branched alkanes at 297 ± 2 K. Int. J. Chem. Kinet. 1984, 16, 469-481.2. Cox, R. A.; Derwent, R. G.; Williams, M. R., Atmospheric photooxidation reactions, reactivity, and mechanism for reaction of organic compounds with hydroxyl radicals. Environ. Sci. Technol. 1980, 14, 57-61.3. Darnall, K. R.; Atkinson, R.; Pitts, J. N., Rate constants for the reaction of the hydroxyl radical with selected alkanes at 300 K. J. Phys. Chem. 1978, 82, 1581-1584.4. Lloyd, A. C.; Darnall, K. R.; Winer, A. M.; Pitts, J. J. N., Relative rate constants for reaction of the hydroxyl radical with a series of alkanes, alkenes, and aromatic hydrocarbons. J. Phys. Chem. 1976, 80, 789-794.5. Greiner, N. R., Hydroxyl Radical Kinetics by Kinetic Spectroscopy. VI. Reactions with Alkanes in the Range 300–500°K. J. Chem. Phys. 1970, 53, 1070-1076.6. Paraskevopoulos, G.; Nip, W. S., Rates of OH radical reactions. VII. Reactions of OH and OD radicals with n-C4H10, n-C4D10, H2 and D2, and of OH with neo-C5H12 at 297 K1. Can. J. Chem. 1980, 58, 2146-2149.7. Atkinson, R.; Aschmann, S. M.; Carter, W. P. L.; Winer, A. M.; Pitts, J. N., Kinetics of the reactions of OH radicals with n-alkanes at 299 ± 2 K. Int. J. Chem. Kinet. 1982, 14, 781-788.8. Tully, F. P.; Koszykowski, M. L.; Stephen Binkley, J., Hydrogen-atom abstraction from alkanes by OH. I. Neopentane and neooctane. Proc. Combust. Inst. 1985, 20, 715-721.9. Nielsen, O. J.; O'Farrell, D. J.; Treacy, J. J.; Sidebottom, H. W., Rate constants for the gas-phase reactions of hydroxyl radicals with tetramethyllead and tetraethyllead. Environmental Science & Technology 1991, 25, 1098-1103.10. Wilson, E. W.; Hamilton, W. A.; Kennington, H. R.; Evans, B.; Scott, N. W.; DeMore, W. B., Measurement and Estimation of Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes and Cycloalkanes. J. Phys. Chem. A 2006 , 110, 3593-3604.11. Darnall, K. R.; Winer, A. M.; Lloyd, A. C.; Pitts Jr, J. N., Relative rate constants for the reaction of OH radicals with selected C6 and C7 alkanes and alkenes at 305 ± 2 K. Chem. Phys. Lett. 1976, 44, 415-418.12. Harris, S. J.; Kerr, J. A., Relative rate measurements of some reactions of hydroxyl radicals with alkanes studied under atmospheric conditions. Int. J. Chem. Kinet. 1988, 20, 939-955.13. Bott, J. F.; Cohen, N., A Shock Tube Study of the Reaction of Methyl Radicals with Hydroxyl Radicals. Int. J. Chem. Kinet. 1991, 23, 1017-1033.14. Baldwin, R. R.; Walker, R. W., Rate constants for hydrogen + oxygen system, and for H atoms and OH radicals + alkanes. J. Chem. Soc., Faraday Trans. 1 1979 , 75, 140-154.15. Badra, J.; Elwardany, A.; Farooq, A., Shock Tube Measurements of the Rate Constants for Seven Large Alkanes + OH. Proc. Combust. Inst. 2014, In Press.16. Koffend, J. B.; Cohen, N., Shock tube study of OH reactions with linear hydrocarbons near 1100 K. Int. J. Chem. Kinet. 1996, 28, 79-87.

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17. DeMore, W. B.; Bayes, K. D., Rate Constants for the Reactions of Hydroxyl Radical with Several Alkanes, Cycloalkanes, and Dimethyl Ether. J. Phys. Chem. A 1999, 103, 2649-2654.18. Donahue, N. M.; Anderson, J. G.; Demerjian, K. L., New Rate Constants for Ten OH Alkane Reactions from 300 to 400 K:  An Assessment of Accuracy. J. Phys. Chem. A 1998, 102, 3121-3126.19. Campbell, I. M.; McLaughlin, D. F.; Handy, B. J., Rate constants for reactions of hydroxyl radicals with alcohol vapours at 292 K. Chem. Phys. Lett. 1976, 38, 362-364.

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