Teorías de contenido

Presented in Tables S.6-8.7 are sensitivity coefficients for selected species for the initial conditions po = 100 torr, To = 581 K and po = 110 torr, To = 515 K respectively. Unfortunately, attempts to include heat losses in SENKIN were unsuccessful and results for the adiabatic case only were possible. As was shown in Chapter 7, heat losses only affected the numerical simulations after the prediction o f the first cool flame. Using this result, the sensitivity coefficients presented in Tables 8.6-8.7 are for two time-points, for a given initial condition, the two time-points denoting the beginning o f the cool flame, i.e. the induction time to a cool flame, and the end o f the cool flame, i.e. the peak temperature o f the cool flame.

The sensitivity coefficients presented in Tables 8.6 and 8.7 are o f the form 5yi/5(lnAj), where yi is the mass fraction o f the i**’ species in the reaction mechanism and Aj = Arrhenius coefficient o f the reaction in the reaction mechanism. The sensitivity coefficient Sÿ (eqn. (5.23), Chapter 5) has been multiplied by Aj to account for any differences in magnitude between Aj, thus allowing comparison o f sensitivity coefficients for a given species. The reaction numbers listed in Tables 8.6 and 8.7 relate to the numerical order in which they are listed in the output o f the Interpreter o f Chemkin-II (see Appendix C). The reactions appearing in Tables 8.6 and 8.7 are also listed, for convenience, in Table 8.8.

The absolute value o f a sensitivity coefficient gives an indication o f how sensitive a given species is to a perturbation in the Arrhenius coefficient o f a certain reaction. The larger the absolute value o f a sensitivity coefficient, the more sensitive species production/consumption is to a particular reaction. The positive or negative sign associated with a given sensitivity coefficient indicates whether a particular reaction increases or decreases the production rate o f the species o f concern. For species acting as reactants in the reaction mechanism, i.e. n-heptane and oxygen, a positive-value sensitivity coefficient indicates that reactant consumption is reduced, while a negative value means that reactant consumption is increased. For all other species, a positive value for a sensitivity coefficient indicates that the species production rate is increased for a perturbation to the Arrhenius coefficient while a negative value decreases the production rate.

n-heptane 4-ketoheptyl-2-hydroperoxide t = rx no 2.4s S t = rx no 3.2s S t rx no = 2.4s S rx no ’ —3.2s S

437 6.68E-02 62 -5.02E-00 437 -1.46E-03 755 -1.90E-01

62 -5.57E-02 20 4.14E-00 62 1.14E-03 62 -3.21 E-02

20 4.66E-02 80 -3.82E-00 80 9.20E-04 20 2.68E-02

80 -4.20E-02 8 -3.05E-00 20 -9.14E-04 80 -2.41 E-02

269 -3.27E-02 269 -2.74E-00 8 7.67E-04 269 -1.99E-02

270 -3.27E-02 270 -2.74E-00 270 6.35E-04 8 -1.83E-02

8 -3.25E-02 437 2.32E-00 269 5.79E-04 270 -1.83E-02

7 2.21 E-02 7 2.05E-00 7 -4.92E-04 7 1.27E-02

18 1.49E-02 18 1.34E-00 168 3.01 E-04 437 -1.04E-02

19 1.49E-02 19 1.34E-00 18 -2.90E-04 18 8.69E-03

56 -1.39E-02 56 -1.29E-00 19 -2.90E-04 19 8.69E-03

168 -1.37E-02 168 -1.28E-00 56 2.70E-04 56 -8.32E-03

503 -1.17E-02 6 8.56E-01 6 -2.41 E-04 168 -7.88E-03

501 -1.12E-02 503 -8.20E-01 503 2.25E-04 503 -5.55E-03

502 -1.1 IE-02 501 -7.84E-01 501 2.15E-04 501 -5.31 E-03

6 9.45E-03 502 -7.75E-01 502 2.12E-04 502 -5.25E-03

12 -8.10E-03 12 -7.1 IE-01 61 -1.76E-04 6 4.97E-03

13 -7.75E-03 13 -6.76E-01 12 1.57E-04 12 -4.64E-03

16 7.17E-03 170 -6.71 E-01 170 1.54E-04 13 -4.43E-03

17 7.17E-03 61 6.51 E-01 13 1.51 E-04 17 4.16E-03

57 -7.15E-03 17 6.44E-01 16 -1.39E-04 16 4.16E-03

170 -7.04E-03 16 6.43E-01 17 -1.39E-04 170 -4.05E-03

61 6.95E-03 57 -6.27E-01 57 1.39E-04 57 -4.03E-03

Table 8.6a Selected sensitivity coefficients with respect to n-heptane and 4-ketoheptyI-2- hydroperoxide. Numerical simulation, po = 100 torr. To = 581 K. Cylindrical batch reactor. Volume = 330 cm^. Heat loss: Adiabatic. Sensitivity coefficients, S, are o f the form 5yi/5(hiAj); y = mass fraction, Aj = Arrhenius coefficient of j* reaction.

Chapter Eight Results and Discussion— Kinetic Analysis

hydrogen peroxide heptyM-hydroperoxide

f =2.4s f = 3.2s t= 2.4s = 3.2s

rx no S rx no S rx no S rx no S

437 -4.53E-04 437 -1.58E-02 437 -6.57E-05 62 -4.21 E-03 62 3.56E-04 62 1.07E-02 62 4.89E-05 437 -3.37E-03 20 -2.87E-04 80 9.30E-03 20 -4.47E-05 20 3.31 E-03 80 2.85E-04 8 9.12E-03 80 4.13E-05 80 -2.99E-03 8 2.33E-04 20 -7.85E-03 8 3.73E-05 269 -2.29E-03 269 2.22E-04 7 -4.88E-03 269 3.21 E-05 270 -2.29E-03 270 2.22E-04 269 4.49E-03 270 3.21 E-05 8 -2.03E-03 7 -1.48E-04 270 4.49E-03 7 -2.37E-05 7 1.48E-03 168 9.30E-05 168 3.46E-03 18 -1.42E-05 18 1.07E-03 18 -9.12E-05 6 -3.21 E-03 19 -1.42E-05 19 1.07E-03 19 -9.12E-05 19 -2.51 E-03 168 1.35E-05 56 -1.04E-03 503 8.20E-05 18 -2.51 E-03 56 1.30E-05 168 -9.74E-04 56 7.99E-05 61 -2.22E-03 6 -1.19E-05 503 -7.11 E-04 501 7.86E-05 170 1.95E-03 503 1.11E-05 501 -6.82E-04 502 7.78E-05 56 1.93E-03 501 1.06E-05 502 -6.74E-04 6 -7.50E-05 57 1.69E-03 502 1.04E-05 12 -5.78E-04 61 -5.33E-05 503 1.62E-03 61 -8.53E-06 13 -5.52E-04 12 4.94E-05 501 1.54E-03 12 7.69E-06 17 5.14E-04 57 4.91 E-05 502 1.53E-03 13 7.36E-06 16 5.14E-04 170 4.78E-05 12 1.29E-03 57 7.03E-06 6 5.06E-04 13 4.73E-05 432 -1.27E-03 170 6.93E-06 170 -4.99E-04 17 -4.37E-05 13 1.22E-03 17 -6.80E-06 57 -4.81 E-04 16 ^.37E-05 16 -1.20E-03 16 -6.80E-06 61 4.10E-04

Table 8.6b Selected sensitivity coefficients with respect to hydrogen peroxide and heptyl-4- hydroperoxide. Numerical simulation, po = 100 torr. To = 581 K. Cylindrical batch reactor. Volume = 330 cm^. Heat loss: Adiabatic. Sensitivity coefficients, S, are o f the form 5yi/ô(lnAj); y = mass fraction, Aj = Arrhenius coefficient o f reaction.

2-methyl-5-ethy tetrahydrofuran hept-3-ene

t = 2.4s f =3.2s t= 2.4s = 3.2s

rx no S rx no S rx no S rx no S

437 -2.32E-02 62 1.70E-00 437 -1.18E-03 437 -2.56E-02 62 1.93E-02 20 -1.40E-00 62 8.98E-04 8 1.92E-02 20 -1.62E-02 80 1.29E-00 80 7.44E-04 80 1.48E-02 80 1.46E-02 8 9.94E-01 20 -7.03E-04 62 1.35E-02 269 1.14E-02 269 9.29E-01 8 6.54E-04 7 -8.97E-03 270 1.14E-02 270 9.29E-01 269 5.79E-04 6 -8.00E-03 8 1.02E-02 437 -7.96E-01 270 5.79E-04 20 -7.52E-03 7 -6.06E-03 7 -6.39E-01 7 -4.03E-04 269 6.15E-03 56 5.44E-03 56 4.61 E-01 19 -2.65E-04 270 6.15E-03 18 -5.22E-03 18 -4.56E-01 168 2.43E-04 168 5.68E-03 19 -5.22E-03 19 -4.56E-01 18 -2.22E-04 19 -5.49E-03 168 4.76E-03 168 4.34E-01 6 -2.22E-04 61 -4.62E-03 503 4.04E-03 6 -2.98E-01 56 2.21 E-04 170 3.26E-03 501 3.88E-03 503 2.78E-01 503 2.07E-04 56 3.05E-03 502 3.85E-03 501 2.65E-01 501 1.98E-04 16 -2.60E-03 6 -3.58E-03 502 2.62E-01 502 1.96E-04 17 -2.60E-03 12 2.82E-03 12 2.41 E-01 61 -1.48E-04 12 2.59E-03 13 2.71 E-03 13 2.30E-01 12 1.43E-04 57 2.31 E-03 16 -2.49E-03 170 2.27E-01 16 -1.27E-04 503 2.31 E-03 17 -2.49E-03 61 -2.21 E-01 17 -1.27E-04 501 2.16E-03 170 2.44E-03 17 -2.18E-01 13 1.26E-04 502 2.15E-03 61 -2.41 E-03 16 -2.18E-01 170 1.25E-04 18 -1.95E-03 57 2.21 E-03 57 2.02E-01 57 1.23E-04 169 1.83E-03

Table 8.6c Selected sensitivity coefficients with respect to 2-methyl-5-ethyl tetrahydrofuran and hept-3-ene. Numerical simulation, po = 100 torr. To = 581 K. Cylindrical batch reactor. Volume = 330 cm^. Heat loss: Adiabatic. Sensitivity coefficients, S, are of the form 5yi/5(lnAj); y = mass fraction, Aj = Arrhenius coefficient o f j* reaction.

Chapter Eight Results and Discussion— Kinetic Analysis

hept-2-Yl radical hept-4-i/! radical

f = rx no 2.4s S f = rx no 3.2s S t rx no = 2.4s S rx no t = 3.2s S 437 -6.56E-08 437 6.09E-06 437 -4.05E-07 437 2.81 E-05

62 5.46E-08 62 ^.94E-06 62 3.00E-07 62 -2.30E-05 20 -4.56E-08 20 4.07E-06 20 -2.85E-07 20 1.88E-05 80 4.12E-08 80 -3.78E-06 80 2.55E-07 80 -1.74E-05 269 3.18E-08 8 -3.03E-06 8 2.38E-07 8 -1.37E-05 270 3.18E-08 269 -2.70E-06 269 1.97E-07 269 -1.24E-05 8 2.92E-08 270 -2.70E-06 270 1.97E-07 270 -1.24E-05 7 -2.47E-08 7 2.01 E-06 7 -1.53E-07 7 9.25E-06 18 -1.46E-08 18 1.32E-06 18 -9.05E-08 18 6.10E-06 19 -1.46E-08 19 1.32E-06 19 -9.05E-08 19 6.10E-06 56 1.37E-08 56 -1.28E-06 56 8.47E-08 56 -5.89E-06 168 1.35E-08 168 -1.27E-06 168 8.33E-08 168 -5.87E-06

503 1.08E-08 6 8.85E-07 6 -7.49E-08 6 3.76E-06

501 1.04E-08 503 -7.82E-07 503 6.72E-08 503 -3.59E-06 502 1.02E-08 501 -7.46E-07 501 6.41 E-08 501 -3.44E-06 13 7.57E-09 502 -7.38E-07 502 6.34E-08 502 -3.40E-06 17 -7.08E-09 12 -7.18E-07 61 -5.31 E-08 12 -3.21 E-06 16 -7.08E-09 170 -6.66E-07 12 4.90E-08 170 -3.08E-06 170 6.92E-09 13 -6.63E-07 13 4.69E-08 13 -3.06E-06 57 6.92E-09 61 6.45E-07 16 -4.34E-08 17 2.92E-06 61 -6.83E-09 17 6.33E-07 17 -4.34E-08 16 2.92E-06 432 -4.55E-09 16 6.33E-07 57 4.28E-08 61 2.92E-06 312 4.12E-09 57 -6.15E-07 170 4.28E-08 57 -2.84E-06

Table 8.6d Selected sensitivity coefficients with respect to hept-2-yI and hept-4-yl radicals.

Numerical simulation. Po = 100 torr. To = 581 K. Cylindrical batch reactor. Volume = 330 cm^. Heat loss: Adiabatic. Sensitivity coefficients, S, are of the form ôyi/ô(lnAj); y = mass fraction, Aj = Arrhenius coefficient ofj^ reaction.

n-heptane 4-ketoheptvl-2-hydroperoxide t = rx no 32s S f = rx no 33s S t rx no = 32s S t rx no = 33s S 62 -3.53E-00 62 6.24E-00 62 1.98E-01 269 -1.54E-08 20 2.74E-00 20 -4.88E-00 20 -1.51 E-01 62 -1.36E-08 269 -2.38E-00 270 4.37E-00 270 1.31 E-01 20 1.22E-08 270 -2.38E-00 269 4.37E-00 269 1.30E-01 80 -1 02E-08 437 2.04E-00 437 -3.49E-00 437 -1.19E-01 8 -9.63E-09 80 -1.73E-00 80 3.01 E-00 8 1.02E-01 437 8.31 E-09 8 -1.69E-00 8 2.79E-00 80 1.00E-01 270 -6.34E-09 7 1.11E-00 7 -1.94E-00 7 -6.53E-02 7 5.57E-09 18 7.46E-01 18 -1.31 E-00 18 -4.09E-02 754 5.00E-09 19 7.46E-01 19 -1.31 E-00 19 -4.09E-02 18 4.33E-09 12 -6.99E-01 12 1.25E-00 12 3.84E-02 19 4.33E-09 13 -6.92E-01 13 1.25E-00 13 3.80E-02 56 -4.25E-09 503 -6.38E-01 503 1.15E-00 503 3.49E-02 12 -2.83E-09 501 -6.26E-01 501 1.12E-00 501 3.42E-02 13 -2.63E-09 502 -6.23E-01 502 1.12E-00 502 3.41 E-02 6 2.53E-09 56 -5.77E-01 56 1.02E-00 6 -3.30E-02 61 2.36E-09 6 5.29E-01 6 -8.44E-01 56 3.17E-02 17 2.33E-09 17 4.28E-01 475 -7.76E-01 61 -2.47E-02 16 2.32E-09 16 4.28E-01 17 -7.51 E-01 17 -2.35E-02 750 -2.23E-09 61 3.99E-01 16 -7.51 E-01 16 -2.35E-02 267 -1.76E-09 475 3.94E-01 61 -6.61 E-01 475 -2.19E-02 268 1.76E-09 14 -3.50E-01 14 6.26E-01 14 1.92E-02 57 -1.71 E-09 57 -2.74E-01 57 4.60E-01 57 1.50E-02 50 -1.68E-09 312 -2.24E-01 312 4.11 E-01 312 1.23E-02 259 1.54E-09 168 -2.08E-01 168 3.35E-01 168 1.23E-02 260 -1.54E-09

Table 8.7a Selected sensitivity coefUcients with respect to n-heptane and 4-ketoheptyl-2-

hydroperoxide. Numerical simulation, po = 110 torr. To = 515 K. Cylindrical batch reactor. Volume = 330 cm^. Heat loss: Adiabatic. Sensitivity coefficients, S, are of the form 5yj/5(lnAj); y = mass fraction, Aj = Arrhenius coefficient of reaction.

Chapter Eight Results and Discussion— Kinetic Analysis

hydrogen peroxide heptvl-4-hvd roperoxlde f =32s f =33s t = 32s t= 33s

rx no S rx no S rx no S rx no S

62 1.31E-02 62 -3.20E-02 62 2.85E-02 62 -8.48E-10 20 -9.97E-03 20 2.85E-02 20 -2.26E-02 437 5.55E-10 269 8.93E-03 269 -2.57E-02 269 1.99E-02 45 -5.41 E-10 270 8.93E-03 270 -2.57E-02 270 1.99E-02 20 4.10E-10 437 -7.66E-03 80 -9.67E-03 437 -1.71E-02 80 -4.09E-10 80 6.50E-03 437 8.38E-03 8 1.50E-02 754 3.60E-10 8 6.42E-03 56 -8.24E-03 80 1.45E-02 269 -2.06E-10 7 -4.15E-03 18 8.05E-03 7 -9.67E-03 270 -2.06E-10 18 -2.71 E-03 19 8.05E-03 18 -6.14E-03 750 -1.94E-10 19 -2.71 E-03 7 8.03E-03 19 -6.14E-03 8 -1.87E-10 12 2.55E-03 12 -7.43E-03 12 5.76E-03 56 -1.61 E-10 13 2.52E-03 13 -7.31 E-03 13 5.70E-03 7 1.61 E-10 503 2.41 E-03 503 -5.99E-03 503 5.28E-03 19 1.51E-10 501 2.36E-03 501 -5.89E-03 501 5.17E-03 18 1.51E-10 502 2.35E-03 502 -5.86E-03 502 5.15E-03 40 1.24E-10 6 -2.06E-03 17 4.61 E-03 6 ^.86E-03 39 1.24E-10 56 2.06E-03 16 4.61 E-03 56 4.74E-03 41 1.24E-10 17 -1.56E-03 475 3.85E-03 61 -3.64E-03 503 1.22E-10 16 -1.56E-03 14 -3.64E-03 17 -3.52E-03 12 -9.67E-11 475 -1.55E-03 8 -2.84E-03 16 -3.52E-03 475 9.47E-11 61 -1.54E-03 747 -2.76E-03 14 2.89E-03 13 -9.06E-11 14 1.28E-03 312 -2.47E-03 475 -2.33E-03 25 -8.64E-11 57 1.05E-03 50 -1.64E-03 57 2.31 E-03 168 -8.55E-11 312 8.70E-04 4 -1.06E-03 312 1.89E-03 17 8.19E-11 168 7.81 E-04 2 -1.05E-03 168 1.75E-03 16 8.18E-11

Table 8.7b Selected sensitivity coefficients with respect to hydrogen peroxide and heptyl-4- hydroperoxide. Numerical simulation, po = 110 torr. To = 515 K. Cylindrical batch reactor. Volume = 330 cm^. Heat loss: Adiabatic. Sensitivity coefficients, S, are o f the form 0y/6(lnAj); y = mass fraction, Aj = Arrhenius coefficient o f j* reaction.

Reaction Reaction num ber 437 62 20 80 2 6 9 270 18 19 56 168

Y Y v

X ?