The Thermal Decomposition of n-Hexane

K. H. EBERT, H. J. EDERER, and G. ISBARN

Institut fur Angewandte Physikalische Chemie und Sonderforschungsbereich 123,
Uniuersitat Heidelberg, Heidelberg, Germany

Abstract
The kinetics of the pyrolysis of n-hexane was studied in a conventional static reactor over
a temperature range of 650-840 K. The overall reaction is essentially first order with the
kinetic parameters A = 1013,g2 s-l and E A = 260.3 kJ/mol. The distributions of the main
products were analyzed by gas chromatography. A reaction model involving 240 elementary
reactions was developed to describe the experimental rate data. The agreement of the model
with experimental data was surprisingly good over a wide range of temperatures and pressures
and up to medium extents of conversion. Methods for sensitivity studies based upon the
quasi-stationary-state assumption (QSSA) were developed, and for a number of more detailed
effects, such as self-inhibition, explanations could be given. It was also shown that the hexyl
isomerization reactions influence strongly the product distribution. The outstanding ca-
pability of kinetic modeling with computer simulations in handling complex kinetic systems
is demonstrated.

Introduction
Only a few investigations are published on the homogeneous gas-phase
pyrolysis of n-hexane [l-61. It has been generally accepted that the re-
action proceeds via a complicated radical chain mechanism. Simple re-
action models, based on a small number of elementary reactions, have been
proposed by Frey and Hepp [l]and Chrysochoos and Bryce [5]. However,
a complete description of the experimental results by a reaction mechanism
requires the consideration of a large number of product reactions, which
become important even at low conversions. Because of the complex nature
of the chemical reactions involved, an improvement in the understanding
of the reaction mechanism can only be obtained with the results of reliable
experiments combined with computer simulations.

Description of the Method

The experimental results on the pyrolysis of n-hexane reported in the
literature [ 1-61 are somewhat contradictory, so that new experiments were
carried out in the present work.
Based on these experiments, a reaction model has been developed con-

International Journal of Chemical Kinetics, Vol. 15,475-502 (1983)

0 1983 John Wiley & Sons, Inc. CCC 0538-8066/83/050475-28$03.80
476 EBERT, EDERER, AND ISBARN

sisting of elementary reactions. Simulations of the reaction behavior of

the n-hexane pyrolysis were done with a rather small set of 35 elementary
reactions. Thereby the influence of radical isomerization reactions and
the radical recombination reactions on the overall reaction rate, as well as
on the product distribution, was studied. This model was then extended
by the stepwise addition of further elementary reactions in order to consider
the reactions of the products formed in the initial stage of the pyrolysis.
Developing a reaction model in this way has the advantage that the influ-
ence of particular elementary reactions on the overall reaction behavior
becomes obvious. Adjustment of the kinetic parameters of the elementary
reactions has been carried out with care and within the limits given in the
literature. Trial and error methods, sometimes with support of sensitivity
analysis, were used.
The simulation of a complex chemical reaction system, mathematically
described by a system of ordinary differential equations (ODES),requires
special numerical methods because of the stiffness of the ODE system.
Stochastic methods [7-91, quasi-stationary-state assumption (QSSA)
methods [lo-141, and a considerable number of numerical integration
procedures [15-191 have been applied to such systems. We used different
numerical integration methods in the earlier stage of the work, a program
package including the stiff solver DIFSUB of Gear [ZO], and later adapted
the new, very efficient program package LARKIN of Deuflhard, Bader,
and Nowak [21], which is based on a semi-implicit extrapolation method.
For our experimental reaction conditions the results obtained with the
numerical calculation of a stiff solver and those by the QSSA method agreed
very well. Because the QSSA requires less computer time, we used this
approximation also in calculating the sensitivity matrices (dcildkj, i = 1,
. . . , nspecies, j = 1, . . . , nequations). The quasi-stationary concentrations
of the free radicals are calculated with a multidimensional Newton method
1221.

Experimental

Apparatus
The pyrolysis was carried out in a conventional static system. A quartz
reaction vessel1 of a l-L volume was housed in an electrically heated
stainless-steel block.

* Data at lower temperatures (650-720 K) were obtained using a Duran glass cylinder of
similar volume. After pretreating the vessels sufficientlylong with reaction products,a coating
was obtained. Therefore no differences were observed in the reaction behavior in both reactors
so that data from both reactors were used without corrections.
 THERMAL DECOMPOSITION OF n-HEXANE 477

Reagents
n-Hexane used in the experiments was high purity (99.5%)material from
Fluka.

Procedure
The overall reaction rate was determined by measuring the total pressure
rise with a quartz spiral gauge and an electrical pressure transducer. Data
were read from a digital multimeter or recorded by a digital tape recorder,
which allowed the monitoring of rather rapid reactions because of its high
reading frequency. Therefore it was possible to work with this static re-
actor at higher temperatures (up to 840 K). The reaction products were
analyzed using a glass sampling valve directly connected to a gas chroma-
tograph. Separations were performed on an alumina column, 2 m by %
in., using a temperature program from 60 to 350C. The quantitative
evaluation of the chromatograms was done using the relative molar response
factors published by Rosie and co-workers [23-251.

Results
Pressure Measurement
The pressuretime curve (Fig. 1)can be divided into three sections: the
initial section showing a strong curvature, followed by a section with
only a slight curvature, and a final section BC with a continuously de-

Figure 1. Plot of pressure rise (728 K). Insert: enlargement of initial period. 0, A , B ,
C-see text.
478 EBERT, EDERER, AND ISBARN

0.0 1.0 2.0

DP

Figure 2. Plot of n-hexane conversion H versus relative pressure rise DP. Dots = experi-
ments; solid line, by regression analysis.

creasing slope. Sections and BC will be discussed later. Section a,

chosen as the linear part from a logarithmic concentration-time plot, was
used for the calculation of the first-order rate constant. Within this section,
the expansion factor E , which is the average number of moles produced by
the decomposition of 1 mol of n-hexane, is about 2.4. The rate of total
pressure rise was evaluated by a nonlinear least-squares procedure [26],
resulting in an overall reaction order of unity. By correlating the n-hexane
conversion H (from analysis) and the relative pressure rise DP [eq. (l)], an
empirical expression connecting conversion H with the relative pressure
rise DP [eq. (2)], valid over the whole temperature range investigated (Fig.
2), was obtained:
DP = (Pt - P o )
Po
where p t is the total pressure at time t and po the initial pressure at t = 0,
and
(2) H = 0.752 * DP - 0.115 DP2 -
The Arrhenius parameters of the overall rate of n-hexane removal, in the
temperature range of 650-840 K obtained by a weighted least-squares
procedure [27], are logloA [s-l] = 13.92 0.14 (0.07; 57; 95%),2and EA [kJ/
moll = 260.3 f 2.0 (1.0; 57; 95%): which are in good agreement with values
given in the literature (Fig. 3).
2 Numbers in parentheses are: standard deviation, number of experiments, and confidence
level.
 THERMAL DECOMPOSITION OF n-HEXANE 479

Y t
b

,{his work
-5 - ,
\
'\

Figure 3. Survey of overall first-orderrate constants. 0-0 Temperaturerange of literature

data; 0-0 temperature range of this work. References: 1--[2a]; 2--[2b]; 3-[28a]; 4-[5];
6--[28b]; 7-[28~]; 8-[28d].

Product Distribution
The analysis of the reaction products has been limited to the major
products. Hydrogen and substances with a molecular weight higher than
that of toluene could not be detected with the gas-chromatographic con-
ditions used. The formation of the products is shown in Figures 4 and 5
as a function of reaction time and relative pressure rise. Concentrations
are given relative to the initial concentration of n-hexane:

(3) conci =- ci x 100

C'hexane
which were obtained by combining analytical results with pressure mea-
surements. The resulting product distribution is shown in Figure 6 and
is in good agreement with [l] and [6], but not with [5]. It may be that the
latter measurements are less reliable.
The products can be divided into those whose concentrations increase
continuously throughout the reaction (methane, ethane, propane, benzene,
toluene) and those whose concentrations pass through a maximum (ethylene,
propene, 1-butene, 1,3-butadiene,1-pentene). The increase in the methane
and ethane concentrations is rather large after the complete conversion of
n-hexane (Fig. 4),corresponding to a strong decrease in the alkene con-
centrations. This point will be discussed later.
480 EBERT, EDERER, AND ISBARN

3
150 -
0 -
U

100 -

0.0 1.0 2.0

DP

Figure 4. Plot of relative concentration versus relative pressure rise DP at 810 K. 1-

Methane; 2-ethane; 3-ethylene; 4-propene; 5-butene; 6-benzene; a-experimental
points; solid lines-connection of experimental points.

An example of the temperature dependence of the product distribution

(evaluated at a relative pressure rise of DP = 0.5) is given in Table I together
with the corresponding results of the simulations. There are no significant
variations in the amounts of propene, benzene, and toluene, and only a
slight variation in the amounts of methane, propene, and 1-butene. A
rather high temperature dependence of ethane and ethylene production
was found. The relative amount of ethane decreases with increasing
temperature, corresponding to an increase in the amount of ethylene. This
behavior is particularly noted in regions of higher conversions (DP 2 1).
Furthermore, the maximum of ethylene formation is shifted toward higher
conversions with increasing temperature.

Influence of Initial Pressure

The relation between the overall reaction rate and the initial n-hexane
pressure has been investigated at 837 K. The initial overall rate ro
(mbar/min) as a function of the initial pressure (mbar) is shown in Figure
7.
 THERMAL DECOMPOSITION OF n-HEXANE 481

150 l------

I CY

6
0 5 ,
0 100 200
t Imin]
Figure 5. Plot of relative concentrations versus reaction time at 810 K. For notation see
Figure 4.

The slope of the plot represents the overall reaction order. The exper-
imental data fit first-order kinetics (solid line) rather well in the upper
pressure region. This result is in agreement with [29] and [30]. The as-
sumption of first-order kinetics in this area is indeed a good approximation.
The pressure dependence of the product distribution is given in Table I1
together with the results of the simulations.
At low initial pressures of n-hexane, the amount of product alkanes de-
creases. This behavior can be explained by the molecularity of the for-
mation reactions of the products: alkanes are formed by bimolecular re-
action steps, whereas alkenes are formed mainly by unimolecular radical
decomposition reactions, whose relative frequency increases with decreasing
pressure. This behavior is in agreement with the results of the computer
simulations.

Discussion
The form of the pressure-time plot (Fig. 1)-strong pressure rise in the
initial section followed by first-order overall kinetics-may be explained
by the following reasons:
 EBERT, EDERER, AND ISBARN

0.0 1.0 2.0

DP

Figure 6. Plot of product distribution versus relative pressure rise DP at 810 K. For notation
see Figure 4.

(1) Alkenes, which are present in a very low concentration, exert already
strong inhibitory effects.
(2) An additional heterogeneous initiated decomposition reaction with
a higher reaction rate in the initial phase.
(3) Reactions of traces of oxygen, possibly within heterogeneous reaction
steps.

I. Product distribution (in mol-% of products) a t DP = 0.5. e-Ex-

TABLE
periments; s-simulation.

711 K e 26.2 16.7 23.3 2.2 21 .I 10.3

s 29.6 16.2 23.5 1.3 20.8 8.6

728 K e 26.2 15.6 25.3 1.9 2 1 .I 9.8

s 29.7 14.6 24.4 1.0 21.3 9.0

750 K e 25.9 14.1 26.7 1.5 21.4 9.5

s 29.7 13.0 25.2 0.7 21.9 9.5

766 K e 25.8 14.4 27.9 1.2 2 1 .8 8.6

s 29.7 12.1 25.7 0.5 22.3 9.7

 THERMAL DECOMPOSITION OF n-HEXANE 483

0.0' ' ' " I ' " '

1.0 2.0
log Po
Figure 7. Plot of initial rate ro versus initial n-hexane pressure PO. A-[30], 830 K 0-[29],
830 K; X-this work, 837 K; straight line-overall reaction order n = 1.

(4) An additional temperature effect due to rather slow equilibration

of the reaction temperature.
Simulations of our reaction model confirm that inhibition reactions of
alkenes indeed influence the reaction behavior even in regions of very low
conversions.
The decrease of the rate of pressure rise to somewhat less than calculated
from first-order kinetics can be explained by assuming the involvement
of inhibition reactions and product reactions forming polymeric, cyclic, and
aromatic compounds. A comparison of the experimental and the simulated
pressure rise values is given in Figure 8.
A reaction model for the thermal decomposition of n-hexane, based on
240 elementary reactions, was developed [14] (Table 111). A great number
of product reactions, which proved to be important already in the initial
stages of the reaction, were included. The handling of such a huge reaction
system is only possible by computer simulation. This allows a detailed
discussion of the influence of particular elementary reactions on the overall
reaction behavior as well as on the product distribution, that is, it can be
shown easily whether or not a specific elementary reaction influences the
overall reaction behavior. It is essential that the model contains all ele-
mentary reactions that determine the reaction properties within the ex-
perimental conditions under consideration. Most of the kinetic parameters
of the elementary reactions were taken from the literature [31]. A com-
pilation of all kinetic data on thermal hydrocarbon elementary reactions
published up to 1980 is available [32]. Data not available were estimated,
484 EBERT, EDERER, AND ISBARN

TABLE11. Product distribution (in mol-% of products) at 837 K, t =

5 min, versus initial pressure PO. e-Experiments; s-simulation.

0.7 S 27. 9 2.3 38. 7 24.9 6.0

16.6 e 25.7 8.4 34.2 22.2 5.5

21.8 S 31.5 6. 7 31.9 23.9 5.9

45.3 e 28.3 11.1 35.5 22.9 0.9

50.8 S 31 . 4 8.4 29.8 23.4 6.8

7 1 .O e 27.9 10.6 35.4 22.7 1.3

79.8 S 31.4 9.3 28.9 23.1 7.1

96.2 e 28.0 10.8 33.0 20.9 7.1

108.8 S 31.5 10.0 28.4 22.8 7.1

122.1 e 27.3 11.1 32.5 22.0 6.5

137.9 S 31.5 10.5 28.1 22.7 7. I

152.4 S 31.6 10.7 27.9 22.6 7.0

158.3 e 27.2 11.6 32.6 20.1 6.4

166.9 s 31.6 10.9 27.8 22.5 7.0

181.4 S 31.7 11.3 27.6 22.4 6.8

211.8 e 28.1 12.2 30.4 20.8 7.3

considering structural analogy and thermodynamics. Necessary adjust-

ments or selections of kinetic parameters given in the literature were made
considering the following principle: no or only small adjustments of kinetic
parameters that are well established, but allowing for larger variations of
those parameters whose literature values are considered more uncertain.
In the following sections some specific problems are treated by comparing
experimental results and model simulations.

fsomerization Reactions of the Hexyl Radicals

Kossiakoff and Rice [33], studying the hexane pyrolysis, have already
shown that considering the radical isomerization reaction 1-hexyl+2-hexyl
to proceed via a six-center transition state leads to a vast improvement in
the calculated results of the product distribution. A comparison of the
experimental product distribution with a simple stochiometric treatment
 THERMAL DECOMPOSITION OF n-HEXANE 485

0.0
0 500 lo00
t [minl

Figure 8. Plot of relative pressure rise DP at 728 K. See Fig. 1. Solid line = experiment;
X-simulated data.

of the decomposition reactions of the different hexyl radicals showed that

the ratio of the molar flux converted via the four different hexyl-decom-
position reactions no. 167 to no. 170 in Table I11 is approximately:

no. 167:no. 16830. 169110. 170 = 90:50:24:17

(at 711 K and DP = 0.5). This is in good agreement with the integrated
reaction rate values in Table 111,which represent the total flux via the el-
ementary reaction concerned. Hexyl radicals are formed mainly by me-
tathesis reactions of ,&radicals with n-hexane. But the concentrations of
the hexyl radicals formed in this way cannot fully explain the ratios given
above. Therefore it was assumed that isomerization reactions of the hexyl
radicals take place. Although the isomerization reaction l-hexyl + 3-hexyl
is less probable for geometric reasons, it cannot be neglected. This result
was also confirmed by the model simulations and sensitivity analysis (Table
111).

Pentene Formation
In stochiometric calculations and early model simulations the concen-
tration of l-pentene was found to be much higher than experimentally
determined. This led to the assumption that reactions of products formed
in the initial stages of the pyrolysis are also important.
Decomposition of l-pentene and metathesis reactions of p radicals with
1-pentene result in a rapid consumption of l-pentene. The decomposition
of l-pentene does not only influence the product distribution, but it also
accelerates the overall reaction. Thus the formation of 1-pentene due to
 rp
TABLE111. Reaction mechanism for the thermaLdecomposition of n-hexane, with kinetic parameters and numerical values of integrated reaction rates
and relative sensitivities for a selected run a t 711 K and 100,000-sreaction time. (Units: mol, L, cal, K.)
8
.NO REACTIONS LOG A E I-RATES RELATIVE S E N S I T I V I T I E S * 1 0 0 0
(711K , 1 0 0 0 0 0 SEC)
INITIATION CH4 C2H6 C2H4 C3H8 C3H6 C4H8 PENT HEXA PRES

1 CH4 => H + CH3 15.3 1 0 4 0 0 0 .98E-15 0 0 0 0 0 0 0 0 0 1

2 C2H6 => H + C2H5 16.0 98000 .23E-12 0 0 0 0 0 0 0 0 0 2
3 C2H6 => CH3 + CH3 16.6 88000 l l E - 0 8
. 0 0 0 0 0 0 0 0 0 3
4 C3H8 => H + 1-C3H7 16.0 98000 .18E-13 0 0 0 0 0 0 0 0 0 4
5 C3H8 => CH3 + C2H5 16.3 8 5 0 0 0 .36E-09 0 0 0 0 0 0 0 0 0 5 M
6 C4H10 => CH3 + 1-C3H7 16.3 8 5 0 0 0 .55E-12 0 0 0 0 0 0 0 0 m
O 6 n
7 C4H10 = > C2H5 + C2H5 16.3 81400 .70E-ll 0 0 0 0 0 0 0 0 0 7 Y
8 C6H14 => CH3 + 1 - C S H l l 17.2 8 5 4 0 0 .37E-06 12 12 13 12 16 1 7 -10 -11 11 8 "4
9 C6H14 => C2H5 + 1-C4H9 16.5 8 2 4 0 0 .62E-06 19 21 23 19 26 2 3 -18 -20 18 9
1 0 C6H14 = > 1-C3H7 + 1-C3H7 16.1 8 2 4 0 0 .24E-06 8 8 9 10 10 14 -6 -7 7 10
11 C2H4 => H + C2H3 13.0 1 0 8 0 0 0 .30E-18 0 0 0 0 0 0 0 0 0 11
1 2 C3H6 => H + C3H5 15.0 88000 . 2 9 E - 1 0 0 0 0 0 0 0 0 0 0 12
1 3 C3H6 => CH3 + C2H3 15.5 8 9 0 0 0 .46E-10 0 0 0 0 0 0 0 0 0 13 -B
14 144H8 => CH3 + C3H5 16.0 74000 .28E-05 306 312 340 320 414 2 0 9 -288 - 3 1 3 280 14
1 5 I-C4H8 => H + 1-M-AL 16.0 90000 .78E-13 0 0 0 0 0 0 0 0 0 15
16 145H10 => C2H5 + C3H5 16.6 74800 .16E-05 76 81 86 77 104 1 0 0 -113 -78 71 16
1 7 3-M-C4H8 => C H 3 + 1-M-AL . 16.5 78700 . 4 4 E - l l 0 0 0 0 0 0 0 0 0 17
18 3-M-CSHlO => C2H5 + 1-M-AL 16.5 7 7 0 0 0 .28E-10 0 0 0 0 0 0 0 0 0 18 m
'
1 9 3-M-CSHlO => C2H3 + 2XC4H9 16.5 77000 .28E-10 0 0 0 0 0 0 0 0 0 19 rr-
2 0 C4H6 => C2H3 + C2H3 15.5 70500 .95E-06 38 40 45 40 51 5 3 -36 -39 36 20
2 1 C5H8 => C2H3 + C3H5 15.7 72800 .10E-06 26 27 30 27 35 3 6 -25 -26 24 21
22 C6H10 => C3H5 + C3H5 15.7 7 2 8 0 0 .63E-08 2 2 2 2 3 3 -1 -1 2 22

NO REACTIONS LOG A E I-RATES RELATIVE SENSITIVITIES*lOOO

(711K , 1 0 0 0 0 0 SEC)
HYDR&EN ABSTRACTION CH4 C2H6 C2H4 C3H8 C3H6 C4H8 PENT HEXA PRES

23 H + CH4 => H2 + CH3 11.1 12600 .18E-06 0 0 1 1 0 9 1 0 0 2 3

24 H + C2H6 => H2 + C2H5 11.1 9700 .10E-05 0 - 2 2 - 1 0 7 0 0 1 2 4
25 H + C3H8 => H2 + 1-C3H7 11.1 9700 .78E-07 0 0 0 - 9 0 3 1 0 0 2 5
26 H + C3H8 => H2 + 2-C3H7 11.0 8300 .16E-06 0 0 0 - 2 2 1 0 0 0 0 26
27 H + C4H10 => H2 + 1-C4H9 11.1 9700 .12E-09 0 0 0 0 0 0 0 0 0 2 7
28 H + C4HlO => H2 + 2-C4H9 11.0 8400 .25E-09 0 0 0 0 0 0 0 0 0 2 8
29 H + C6H14 => H2 + 1 - C 6 H 1 3 11.0 9700 .14E-04 4 -1 12 21 9 142 30 -6 9 29
30 H + C6H14 => H2 + 2 - C 6 H 1 3 10.7 8400 .18E-04 5 -2 15 27 11 1 7 9 37 -8 11 30
31 H + C6H14 => H2 + 3-C6H13 10.4 8400 .94E-05 2 0 5 6 2 119 27 -3 5 31
32 H + C2H4 => H2 + C2H3 8.5 4500 .14E-06 0 0 0 0 0 2 0 0 0 3 2
33 H + C3H6 => H2 + C 3 H 5 8.5 4500 .10E-06 0 0 0 0 0 3 0 0 0 3 3
34 H + 1-C4H8 => H2 + 1-M-AL 8.5 4500 .50E-07 0 0 0 0 0 -3 0 0 0 3 4
35 H + 1-C4H8 => H2 + 3-BEN 9.1 11600 .13E-08 0 0 0 0 0 0 0 0 0 3 5
36 H + 1-C5H10 => H2 + 1-E-AL 7.7 4500 .21E-08 0 0 0 0 0 0 0 0 0 3 6
37 H + 1-C5H10 => H2 + 1-M-BEN 8.5 11000 .13E-09 0 0 0 0 0 0 0 0 0 3 7 4
38 H + 1-C5H10 => H2 + 4-PEN 9.0 11600 .28E-09 0 0 0 0 0 0 0 0 0 3 8
39 CH3 + H2 => CH4 + H 9.5 10200 .28E-06 0 0 0 0 0 -4 0 0 0 3 9
40 CH3 + CH4 => CH4 + CH3 8.6 14000 .13E-05 0 0 0 0 0 0 0 0 0 4 0 E
41 CH3 + C2H6 => CH4 + C2H5 9.0 10600 .26E-04 -17 -23 -11 - 1 4 9 -35 -735 -167 36 -23 41 c
~
42 CH3 + C3H8 => CH4 + 1-C3H7 9.0 11500 .10E-05 2 0 2 -114 0 5 1 0 1 4 2
43 CH3 + C3H8 => CH4 + 2-C3H7 8.9 10100 .23E-05 0 3 -4 - 2 7 2 1 0 -66 -10 2 0 43
44 C H 3 + C4H10 => CH4 + 1 - C 4 H 9 9.1 11600 .20E-08 0 0 0 0 0 0 0 0 0 4 4 8
45 CH3 + C4H10 => CH4 + 2-C4H9 8.9 9500 .57E-08 0 0 0 0 0 0 0 0 0 4 5 0
46 CH3 + C6H14 => CH4 + 1-C6H13 9.1 11600 .26E-03 61 35 85 1 5 5 113 7 8 7 236 -77 70 46 6
47 CH3 + C6H14 => CH4 + 2-C6H13 8.9 9500 .73E-03 172 97 238 441 319 2178 652 -216 195 47 0
48 CH3 + C6H14 => CH4 + 3-C6H13 8.6 9500 .37E-03 53 68 3 8 -60 31 2 2 1 5 647 -93 63 48 E
49 CH3 + C2H4 => CH4 + C2H3 8.6 8000 .99E-04 -98 -97 -216 -355 -185-1503 -418 163 -150 49 2
50 CH3 + C3H6 => CH4 + C3H5 7.3 4500 .42E-04 -47 -49 - 1 0 4 -180 -95 -586 -434 85 -73 50
51 CH3 + 1-C4H8 => CH4 + 1-M-AL 7.3 4500 .20E-04 -26 -26 46 -73 -45-1712 -65 39 -17 51 !2
52 CH3 + 1-C4H8 => CH4 + 3-BEN 9.0 11600 .66E-05 -5 -5 1 9 -20 -10 -561 -24 10 -2 5 2
53 CH3 + 1-C5H10 => CH4 + 1-E-AL 7.7 4500 .13E-04 1 2 0 0 0 0 0 -221 0 5 53 g
54 CH3 + 1-C5H10 => CH4 + 1-M-BEN 8.9 9500 .63E-05 -1 -1 1 -7 7 -34 -111 4 0 54 a
55 CH3 + 1-C5H10 => CH4 + 4-PEN 9.1 11600 .22E-05 0 0 1 - 2 3 -8 -43 1 0 55
56 C2H5 + H2 => C2H6 + H 8.5 10800 .12E-06 0 0 0 0 0 0 0 0 0 5 6 k
57 C2H5 + CH4 => C2H6 + CH3 8.0 11000 .16E-04 11 14 7 88 2 1 429 98 -20 14 57 f
58 C2H5 + C2H6 => C2H6 + C2H5 9.0 11500 .78E-04 0 0 0 0 0 0 0 0 0 5 8
59 C2H5 + C3H8 => C2H6 + 1-C3H7 9.1 12600 .36E-05 7 3 7 -288 1 80 1 69 -2
-1 4 5 09
6 3
60 C2H5 + C3H8 => C2H6 + 2-C3H7 8.9 10400 .10E-04 4 17 - 1 3 -958 48 -40
61 C2H5 + C4H10 => C2H6 + 1-C4H9 9.3 12600 .99E-08 0 0 0 0 0 0 0 0 0 6 1
62 C2H5 + C4H10 => C2H6 + 2-C4H9 8.65 10400 .10E-07 0 0 0 0 0 0 0 0 0 6 2
63 C2H5 + C6H14 => C2H6 + 1 4 6 H 1 3 8.0 12600 .72E-04 17 14 19 78 32 385 9 8 -25 21 63
64 C2H5 + C6H14 => C2H6 + 2-C6H13 8.0 10400 .34E-03 81 67 90 371 1 5 3 1820 462 -121 97 64
65 C2H5 + C6H14 => C2H6 + 3-C6H13 7.7 10400 .17E-03 30 40 21 101 37 1 2 5 2 3 2 8 -56 38 65
66 C2H5 + C2H4 => C2H6 + C2H3 8.5 11000 .53E-04 -17 -8 -77 55 -30 371 52 2 1 -30 66 rp
67 C2H5 + C3H6 => C2H6 + C3H5 7.3 4500 .24E-03 -77 -43 -384 342 -159 3016 -679 1 1 0 -148 67 m
4
(continued)
 TARI.E -
-111 \ - o ,
(Continued,fromrnreiiious rnape.)
68 C2H5 + 1-C4H8 => C2H6 + 1-M-AL 7.3 4500 . l l E - 0 3 -74 -59 238 6 2 -112-5835 140 8 3 -16 68
69 C2H5 + 1-C4H8 => C2H6 + 3-BEN 9.0 1 1 6 0 0 .38E-04 -10 -5 95 3 5 -18-1910 33 13 7 69
70 C2H5 + 1-C5HlO => C2H6 + 1-E-AL 7.3 4500 .33E-O4 26 7 3 45 11 2 1 8 -350 -10 16 70
71 C2H5 + 1-C5H10 => C2H6 + 1-M-BEN 8.7 9800 .19E-04 - 1 0 5 7 23 47 -230 3 1 71
72 C2H5 + 1-C5H10 => C2H6 + 4-PEN 8.4 9800 .99E-05 0 0 3 4 12 34 -126 1 1 72
73 1-C3H7 + H2 => C3H8 + H 9.8 1 4 6 0 0 .26E-07 0 0 0 1 0 0 0 0 0 73
74 l-C3H7 + CH4 => C3H8 + CH3 8.3 1 5 0 0 0 .34E-06 0 0 0 4 0 0 - 1 0 0 0 74
75 1-C3H7 + C2H6 => C3H8 + C2H5 8.0 1 0 0 0 0 .40E-05 -8 -3 -8 387 0 -106 - 2 5 4 -5 75
76 1-C3H7 + C3H8 => C3H8 + 2-C3H7 8.0 1 0 0 0 0 .32E-06 0 0 0 - 2 1 -7 -1 0 0 76
77 1-C3H7 + C4H10 => C3H8 + 2-C4H9 8.3 1 0 2 0 0 .91E-09 0 0 0 0 0 0 0 0 0 77
78 1-C3H7 + C6H14 = > C3H8 + 1-C6H13 8.0 12600 llE-04
. 0 1 0 200 S ii 5 -2 1 78
79 1-C3H7 + C6H14 => C3H8 + 2-C6H13 8.0 1040.0 .53E-04 -5 3 -4 948 25 82 25 -12 5 79
80 1-C3H7 + C6H14 => C3H8 + 3-C6H13 7.7 1 0 4 0 0 .26E-04 -4 3 -6 460 6 102 30 -5 1 80
81 1-C3H7 + C2H4 => C3H8 + C2H3 8.0 1 5 0 0 0 .17E-06 0 0 0 1 5 0 -2 0 0 0 81
82 1-C3H7 + C3H6 => C3H8 + C3H5 8.0 9200 .76E-05 -19 -8 -30 789 -6 -117 -72 11 - 1 5 82
83 C2H3 + H2 => C2H4 + H 9.9 7400 .71E-04 56 1 3 9 8 3 80 -846 - 3 1 -47 10 83
84 C2H3 + CH4 => C2H4 + CH3 9.0 1 6 0 0 0 .17E-04 25 25 54 89 46 375 1 0 4 -40 38 84
85 C2H3 + C2H6 => C2H4 + C2H5 9.0 16000 llE-04
. 6 3 26 -18 1 0 -125 -17 -6 11 85
86 C2H3 + C3H8 => C2H4 + 1-C3H7 9.5 1 8 8 0 0 .39E-06 1 1 2 -42 0 8 2 0 1 86
87 C2H3 + C3H8 => C2H4 + 2-C3H7 9.0 1 6 2 0 0 .77E-06 1 2 0 -94 5 -10 0 0 1 87
88 C2H3 + C4H10 => C2H4 + 1-C4H9 9.0 1 8 8 0 0 .17E-09 0 0 0 0 0 0 0 0 0 88
89 C2H3 + C4H10 => C2H4 + 2-C4H9 8.9 1 6 8 0 0 .58E-09 0 0 0 0 0 0 0 0 0 89
90 C2H3 + C6H14 => C2H4 + 1-C6H13 9.0 1 8 0 0 0 31E-04
- 22 17 39 67 4 1 307 8 8 -31 29 90
91 C2H3 + C6H14 => C2H4 + 2-C6H13 8.9 1 6 8 0 0 .57E-04 41 32 73 125 7 6 567 1 6 4 - 5 8 54 91
92 C2H3 + C6H14 => C2H4 + 3-C6H13 8.9 1 6 8 0 0 .57E-04 33 36 53 56 4 5 8 4 3 2 4 2 -54 46 92
93 C2H3 + C3H6 => C2H4 + C3H5 9.5 14500 llE-03
. 14 5 31 22 7 603 -615
- -2 16 93
94 C2H3 + 1-C4H8 => C2H4 + 1-M-AL 8.0 1 3 0 0 0 .48E-05 -1 -1 22 -2 -2 -378 2 2 2 94
95 C2H3 + 1-C5H10 => C2H4 + 1-E-AL 9.0 13000 llE-04
. 18 5 12 19 10 80 -- 2 0 9 -8 13 95
96 C2H3 + l-C5H10 => C2H4 + 1-M-BEN 9.0 1 6 0 0 0 .14E-05 0 0 2 0 3 0 -27 0 1 96
97 C2H3 + 1-C5H10 => C2H4 + 4-PEN 9.0 1 6 0 0 0 .14E-05 0 0 2 0 3 3 -29 0 1 97
98 C3H5 + H2 = > C3H6 + H 9.9 7400 .971-04 116 315 -9 -14 177-2514 511 -105 8 98
99 C3H5 + CH4 => C3H6 + CH3 9.0 1 6 0 0 0 .24E-04 52 54 113 195 104 635 471 -91 80 99
100 C3H5 + C2H6 = > C3H6 + C2H5 9.0 1 6 0 0 0 .16E-04 11 6 54 -47 22 -420 9 5 -14 21 100
101 C3H5 + C3H8 => C3H6 + 1-C3H7 9.0 1 8 8 0 0 .17E-06 1 0 1 -30 0 5 3 0 1 101
102 C3H5 + C3H8 => C3H6 + 2-C3H7 8.9 1 6 2 0 0 .86E-06 1 3 0 -173 1 0 -26 5 0 2 102
103 C3H5 + C4H10 => C3H6 + 1-C4H9 8.6 1 8 8 0 0 .94E-10 0 0 0 0 0 0 0 0 0 103
104 C3H5 + C4H10 => C3H6 + 2-C4H9 8.9 1 6 8 0 0 .77E-09 0 0 0 0 0 0 0 0 0 104
105 C3H5 + C6H14 => C3H6 + 1-C6H13 8.6 1 8 8 0 0 .87E-05 11 9 19 34 21 137 68 -15 14 105
106 C3H5 + C6H14 => C3H6 + 2-C6H13 8.9 16800 .72E-04 90 71 157 280 173 1 1 2 1 560 -134 119 106
107 C3H5 + C6H14 => C3H6 + 3-C6H13 8.9 16800 .72E-04 71 82 112 122 100 1752 740 -125 100 107
108 C 3 H 5 + C2H4 => C3H6 + C2H3 9.5 18000 .19E-04 -2 0 -6 -4 -1 -130 134 1 -3 108
109 C3H5 + C3H6 => C3H6 + C3H5 9.0 14500 .50E-04 0 0 0 0 0 0 0 0 0 109
110 C3H5 + 1-C4H8 => C3H6 + 1-M-AL 7.9 13500 .37E-05 -3 -2 27 -3 -3 -508 28 3 3 110
111 C3H5 + 1-C5H10 => C3H6 + 1-E-AL 9.0 10500 .91E-04 229 68 142 245 130 798-2531 -114 172 111
112 C3H5 + 1 4 5 H 1 0 => C3H6 + 1-M-BEN 9.0 13500 .10E-04 0 0 21 0 42 -33 -339 0 8 112
113 C3H5 + 1-C5H10 => C3H6 + 4-PEN 9.0 13500 .10E-04 0 0 23 0 43 0 -373 0 9 113

NO REACTIONS ILOG A E I-RATES RELATIVE S E N S I T I V I T I E S * 1 0 0 0

(711K , 1 0 0 0 0 0 SEC)
ADDITION CH4 C2H6 C2H4 C3H8 C3H6 C4H8 PENT HEXA PRES

114 H + C2H4 => C2H5 10.6 1600 .14E-03 -84 5 1 -, 1 7 5 -232 -97 850 -122 48 -75 114
115 H + C3H6 => 1-C3H7 9.9 2900 .83E-05 23 -11 51 138 -65 407 74 -8 12 115
116 H + C3H6 => 2x3387 9.9 1200 .27E-04 0 0 0 0 0 0 0 0 0 116 0
117 H + 1-C4H8 => 1-C4H9 9.9 2000 .74E-05 0 1 33 -5 1 -576 0 1 5 117
A
118 H + 1-C4H8 => 2-C4H9 9.9 500 .21E-04 55 -27 47 81 129-1174 109 -. 1 9 3 1 118 6
119 H + 1-C5H10 => 1-C5Hll 9.9 2000 .19E-05 0 0 2 0 3 8 -38 -0 1 119
500 .57E-05 0 0 5 0 11 18 -113 1 2 120
120
121
H + 1-C5H10
H + C2H2
=>
=>
2-C5Hll
C2H3
9.9
10.6 1300 .37E-O6 0 -1 2 0 0 9 0 1 0 121
-2
122 CH3 + C2H4 => 1-C3H7 8.5 7800 .90E-04 -52 20 -59 691 -82 3 7 7 111 15 -30 122 $
123 CH3 + C3H6 => 2-C4H9 8.5 7400 .85E-04 0 0 0 0 -1 16 -1 0 0 123
124 CH3 + C3H6 => I-C4H9 8.5 9100 .25E-04 -3 2 - 2- -4 -7 -43 -6 1 -1 1 2 4
125 CH3 + 1-C4H8 => 3-C5Hll 8.3 7200 .29E-04 0 0 0 0 0 0 0 0 0 125 ;J
126 C H 3 + 1-C4H8 => 2-M-B 8.3 9200 .72E-05 -9 5 0 -17 1 4 -374 -19 4 -2 126
127 CH3 + 1 - C 5 H 1 0 => 3x6813 8.3 7200 .81E-05 -4 3 1 -1 1 82 -106 2 0 127 3
128 CH3 + 1 - C 5 H 1 0 => 2-M-P 8.3 9100 .21E-05 0 0 2 6 3 3 -32 0 1 128
129 C H 3 + C2H2 => C3H5 7.4 7700 .15E-07 0 0 0 0 0 0 0 0 0 129
130 C2H5 + C2H4 => 1-C4H9 7.3 7600 .37E-04 9 -4 -7 16 20 78 18 -3 3 130 3
131 C2H5 + C3H6 => 2-C5Hll 7.1 7500 .18E-04 3 -1 7 18 -6 39 9 0 2 131
132 C2H5 t C3H6 => 2-M-B 7.1 9200 .54E-05 7 -3 1 12 -8 247 13 -2 2 132
133 C2H5 + 1 - C 4 H 8 => 3.C6H13 7.1 7500 .88E-05 8 -3 5 25 9 -174 83 -2 3 133
134 C2H5 + 1-C4H8 => 2-E-B 7.1 9200 .26E-O5 0 0 0 0 0 0 0 0 0 134
135 C2H5 + 1-C5H10 => 4-C7H15 7.1 7500 .25E-05 0 0 0 0 0 0 0 0 0 135
0 ~ ~~~
0 136
136 C2H5 + 1-C5H10 => 2-E-P 7.1 9300 .71E-06 0 0 0 1 0 10 -3
137 C2H5 + C2H2 => 1-M-AL 7.4 7000 .14E-06 0 0 1 0 0 1 0 0 0 137
138 1-C3H7 + C2H4 => 1-C5Hll 7.4 8000 .63E-05 -9 6 -21 -53 2 1 -120 -28 4 -5 138 &
139 1-C3H7 + C3H6 => 2-C6H13 9.1 8600 .14E-03 -95 56 -81 -721 -312 1 3 8 5 418 43 -65 139 a
(continued)
 rp
TABLE111. (Continued from previous page.) W
0
140 C2H3 + C2H4 => 3-BEN 7.0 8000 .50E-04 0 0 0 0 0 0 0 0 0 1 4 0
141 C2H3 + C3H6 => 1-M-BEN 7.0 8000 .35E-04 0 0 0 0 0 0 0 0 0 1 4 1
142 C2H3 + 1-C4H8 => 1-E-BEN 7.0 8000 .16E-04 53 16 -7 58 30-1045 68 -26 25 142
143 C3H5 + C2H4 => 4-PEN 7.7 8000 .36E-03 0 0 0 0 0 0 0 0 0 1 4 3
144 C3H5 + C3H6 => 1-M-PEN 7.0 8000 .50E-04 0 0 0 0 0 0 0 0 0 1 4 4

NO REACTIONS LOG A E I-RATES RELATIVE SENSITIVITIES*lOOO

(711K , 1 0 0 0 0 0 S E C )
RADICAL ISOMERIZATION CH4 C2H6 C2H4 C3H8 C3H6 C4H8 PENT HEXA PRES
f711K , 1 0 0 0 0 0 SEC)
=> 2 - C 5 H l l 11.0 20000 .37E-04 -4 -
3 -10
-. - 2~.
6 ~~ ~~
1 0 -59 - 1 3 2 -2 145
145 1-C5Hll
146 2-C5Hll => 1 - C 5 H l l 11.1 22900 .32E-04 4 -1 10 24 -8 53 13 -1 3 146
147 1-C6H13 => 2 x 6 8 1 3 11.0 13700 llE+00 219 -127 1 8 6 1 6 4 3 711-3147 -949 -97 150 147
148 2-C6H13 => 1 - C 6 H 1 3 11.1 16600 llE+00 -218 1 2 8 -185-1647 - 7 1 2 3 1 5 8 9 5 3 98 - 1 4 9 148
.. -'
149 1-C6H13 => 3-C6H13 11.0 20000 .13E-02 -145 8 7 -363-1258 -577 5 0 4 8 1 4 3 7 6 7 -154 149 m
150 3-C6H13 => 1 - C 6 H 1 3 11.1 22900 .85E-03 93 -54 2 3 1 7 9 9 367-3204 - 9 1 1 - 4 1 98 150

RADICAL DECOMPOSITION E
151 C2H5 => H + C2H4 13.9 41700 .34E-04 4 -1 8 10 4 -37 5 -1 3 151
152 1-C3H7 => H C3H6
+ 13.2 38000 .14E-04 -6 4 -15 -41 20 -124 -22 3 -3 152 5>
153 1-C3H7 => CH3 + C2H4 13.2 32000 .10E-02 155 -58 175-2017 242-1100 - 3 2 3 -43 92 153
154 2-C3H7 => H + C3H6 13.6 40300 .43E-04 0 0 0 0 0 0 0 0 0 154
155 1-C4H9 => H + 1-C4H8 13.0 38000 .91E-07 0 0 0 0 0 3 0 0 0 155
156 1-C4H9 => C2H5 + C2H4 13.6 29000 .21E-03 -25 14 2 1 -43 -54 -214 -48 10 -6 156
157 1-C4H9 => C3H6 + CH3 12.1 21700 .25E-04 26 -13 -20 44 55 2 1 3 49 -9 7 157
158 2-C4H9 => H + 1-C4H8 13.3 39800 .31E-06 0 0 0 0 -1 20 -1 0 0 158
159 2-C4H9 => CH3 + C3H6 13.4 31900 .10E-03 1 0 1 1 2 - 1 9 2 0 1 159
160 I-C4H9 => H + I-C4H8 13.7 36600 .12E-05 -2 -2 - 2- -4 -7 0
- 4.. -6 1 -1 160
161 I-C4H9 => CH3 + C3H6 13.9 33000 .24$-04 3 -1 3 5 8 4 1 7 0 2 161
162 1-C5Hll => 1-C3H7 + C2H4 12.6 28700 .31E-05 5 -2 11 27 -9 60 14 -1 3 162
163 2-C5Hll => C2H5 + C3H6 12.6 27900 .29E-04 -3 2 -9 -23 9 -52 -12 2 -2 163
164 3-CSHll => CH3 + 1-C4H8 13.5 31500 .29E-04 0 0 0 0 0 0 0 0 0 164
165 2-M-B => CH3 + 1-C4H8 13.5 31500 .56E-05 8 -3 1 1 4 -10 303 16 -2 2 165
166 2-M-B => C2H5 + C3H6 12.5 27900 .71E-05 -7 4 0 -13 11 - 3 0 2 -15 3 -1 166
167 146H13 => 1-C4H9 + C2H4 12.6 27900 .19E-03 -72 41 1 7 9 -382 - 1 3 2 - 1 8 9 9 - 4 8 6 31 5 167
168 2-C6H13 => 1-C3H7 + C3H6 12.6 27900 . llE-02 2 1 9 .127 1 8 6 1 6 4 8 713-3157 -952 -97 150 168
169 3-C6H13 => C2H5 + 1-C4H8 12. 6 27900 .78E-03 -265 145 -180 -879 -326 6103-2872 1 1 0 -121 169
170 3-C6H13 = > CH3 + l-CSH10 13.4 31500 .38E-03 174 -88 - 4 9 80 -39-2898 3 7 8 5 -67 23 170
171 2-M-P => 1-C3H7 + C3H6 12.5 27900 .21E-05 0 0 0 0 0 0 0 0 0 171
172 2-E-B = > C2H5 + 1-C4H8 12.5 27900 .26E-05 0 0 0 0 0 0 0 0 0 172
173 4-C7H15 = > C2H5 + 1-C5H10 12.5 27900 .25E-05 0 0 0 0 0 0 0 0 0 173
174 2-E-P => C2H5 + 1-C5H10 12.5 27900 .35E-06 0 0 0 0 0 - 4 2 0 0 174
175 2-E-P => 1-C3H7 + 1-C4H8 1 2 . 5 27900 .35E-06 0 0 0 1 0 5 - 1 0 0 175
176 C2H3 => H + C2H2 9.0 31500 .12E-05 1 1 - 1 0 1 - 7 0 0 1 176
177 C3H5 => CH3 + C2H2 10.5 36200 .18E-05 5 2 3 6 -4 18 14 -2 4 177
178 1-M-AL = > H + C4H6 14.8 49300 .61E-06 1 1 - 1 0 1 - 5 0 0 0 178
179 1-M-AL => C2H3 + C2H4 13.7 38000 .14E-03 55 57 69 58 73 7 5 -55 -57 52 179
180 3-BEN = > C2H3 + C2H4 13.0 34000 .96E-04 0 0 0 0 0 0 0 0 180
181 1-E-AL = > CH3 + C4H6 13.0 32000 .15E-03 0 0 0 0 0 0 0 0 181
182 1-M-BEN = > C2H3 + C3H6 13.0 34000 .74E-04 0 0 0 0 0 0 0 0 182
183 4-PEN => C3H5 + C2H4 13.0 34000 .38E-03 0 0 0 0 0 0 0 0 183
184 1-M-PEN = > C3H5 + C3H6 13.5 26000 .50E-04 0 0 0 0 0 0 0 0 184
185 1-E-BEN => CH3 + C5H8 13.0 34000 .16E-04 0 0 0 0 0 0 0 0 185 8
0
NO REACTIONS LOG A E I-RATES RELATIVE SENSITIVITIES'lOOO
(711K , 1 0 0 000 S E C )
RADICAL RECOMBINATION CH4 C2H6 C2H4 C3H8 C3H6 C4H8 PENT HEXA PRES
2
0
186 H + H => H2 9.0 0.0 .36E-16 0 0 0 0 0 0 0 0 0 186
187 H + C2H3 => C2H4 10.0 0.0 .16E-10 0 0 0 0 0 0 0 0 0 187
188 H + C3H5 => C3H6 10.3 0.0 .39E-10 0 0 0 0 0 0 0 0 0 188 8
189 CH3 + CH3 => C2H6 10.7 0.0 .39E-07 0 0 0 0 0 0 1 1 0 189
190 C H 3 + C2H5 => C3H8 10.5 0.0 .18E-06 -1 -1 -2 0 -2 -2 2 2 -1 1 9 0
191 CH3 + C2H3 => C3H6 10.0 0.0 .99E-07 -2 -3 -3 -3 -3 -4 3 4 -2 191 $
192 C3! + C3H5 => 1-C4H8 10.3 0.0 .24E-O6 .15 - 1 5 - 1 6 -15 - 2 0 - 1 0 15 1 6 -13 192
193 C H 3 + 1-M-AL => 3-M-C4H8 9.5 0.0 .71E-08 0 0 0 0 0 0 0 0 0 193
194 CH3 + 1-E-AL => 3-M-CSH10 9.5 0.0 .52E-09 0 0 0 0 0 0 0 0 0 194
195 C2H5 + C2H5 => C4H10 9.6 0.0 .17E-06 0 0 0 0 - 1 - 1 1 1 0 195
196 CZH5 + C2H3 => 1 4 4 H 8 9.0 0.0 .623-07 -1 -1 -1 -1 -1 ' 0 1 2 0 196
197 C2H5 + C3H5 => 1 - C 5 H 1 0 9.5 0.0 .23E-06 -10 -11 - 1 2 -10 -14 -14 17 11 -9 197
198 C2H5 + 1-M-AL => 3-M-CSH10 9.0 0.0 .13E-07 0 0 0 0 0 0 1 1 0 198
199 C2H5 + 1-E-AL => TAR 9.0 0.0 .10E-08 0 0 0 0 0 0 0 0 0 199
200 1-C3H7 + 1-C3H7 = > C6H14 9.5 0.0 .29E-08 0 0 0 0 0 0 0 0 0 200
201 C2H3 + C2H3 => C4H6 10.1 0.0 .21E-05 -88 -93 -105 - 9 2 -118 - 1 2 3 88 9 4 -82 201
202 C2H3 + C3H5 => C 5 H 8 9.0 0.0 .22E-06 -15 -16 -18 -16 -22 -22 17 1 7 -14 202 4
203 C2H3 + 1-M-AL => C6H10 9.0 0 . 0 .40E-07 -1 -2 -2 -2 -2 -2 2 3 -1 2 0 3 2
(continued \
 3!
-4
m
TABLE111. (Continuedfrom previous page.)
Bz
204 C3H5 + C3H5 => C6H10 9.5 0.0 .95E-06 -118 - 1 2 3 - 1 3 3 - 1 2 3 - 1 6 9 - 1 7 3 1 2 7 1 2 4 -109 204
205 C3H5 + 1-M-AL => TAR 8.5 0.0 .17E-07 -1 -1 -1 -1 -1 -2 2 2 -1 2 0 5 -8
206 C3H5 + 1-E-AL => TAR 8.5 0.0 .12E-08 0 0 0 0 0 0 0 0 0 2 0 6 >
207 1-M-AL + 1-M-AL => TAR 8.5 0.0 .30E-08 0 0 0 0 0 0 0 0 0 2 0 7
208 1-M-AL + 1-E-AL => TAR 8.5 0.0 .22E-09 0 0 0 0 0 0 0 0 0 2 0 8 ~
209 1-E-AL + 1-E-AL = > TAR 8.5 0.0 .17E-10 0 0 0 0 0 0 0 0 0 2 0 9

RADICAL D I S PROPORTIONAT ION $

210 CH3 + C2H5 => CH4 + C2H4 8.4 0.0 .14E-08 0 0 0 0 0 0 0 0 0 2 1 0
z
211 CH3 + C2H3 => CH4 + C2H2 9.0 0.0 .99E-08 0 0 0 0 0 0 0 0 0 2 1 1
212 CH3 + C3H5 => CH4 + C3H4 9.0 0.0 .12E-07 0 0 0 0 0 0 1 1 0 2 1 2
213 CH3 + 1-M-AL => CH4 + C4H6 9.9 0.0 .17E-07 0 0 0 0 0 0 1 1 0 2 1 3
214 C2H5 + C2H5 => C2H6 + C2H4 7.1 0.0 .21E-08 0 0 0 0 0 0 0 0 0 2 1 4
215 C2H5 + C2H3 => C2H6 + C2H2 8.0 0.0 .62E-08 0 0 0 0 0 0 0 0 0 2 1 5
216 C2H5 + C2H3 => C2H4 + C2H4 8.5 0.0 .19E-07 0 0 0 0 0 0 0 1 0 2 1 6
217 C2H5 + C3H5 => C2H6 + C3H4 8.6 0.0 .29E-07 0 0 -1 0 -1 -1 1 1 0 217
218 C2H5 + C3H5 => C2H4 + C3H6 8.6 0.0 .29E-07 0 0 -1 0 -1 -1 1 1 0 218
219 C2H5 t 1-M-AL => C2H6 + C4H6 9.1 0.0 .17E-07 0 0 0 0 0 0 1 1 0 2 1 9
220 C2H5 + 1-M-AL => C2H4 + 1-C4H8 8.5 0.0 .43E-08 0 0 0 0 0 0 0 0 0 2 2 0
221 C2H3 + C2H3 => C2H4 t C2H2 9.5 0.0 .54E-06 -21 -23 -25 -22 -29 -30 22 24 -20 221
222 C2H3 + C3H5 = > C2H4 + C3H4 9.0 0.0 .22E-O6 -15 -16 -17 -16 -22 -22 17 1 7 -14 222
223 C2H3 + 1-M-AL => C2H4 + C4H6 9.0 0.0 .40E-07 -1 -2 -2 -2 -2 -2 2 3 -1 223
224 C3H5 + C3H5 => C3H6 + C3H4 9.5 0.0 .95E-06 -118 - 1 2 3 - 1 3 3 - 1 2 3 - 1 6 2 - 1 7 3 127 1 2 4 -108 224
225 C3H5 + 1-M-AL => C3H6 + C4H6 9.8 0.0 .34E-06 -34 -36 -41 -36 -46 -49 36 37 -32 225
226 C3H5 + 1-M-AL => C3H4 + 1-C4H8 9.0 0.0 .54E-07 -5 -5 -6 -5 -7 -2 6 6 -4 226
227 1-M-AL + 1-M-AL = > C4H6 + 1-C4H8 9.5 0.0 .30E-07 -2 -2 -2 -2 -2 0 3 3 -1 227

AROMATI ZATION

2 2 8 C4H6 + C2H4 => C H 7.5 2 7 5 0 0 .45E-04 0 0 -93 0 0 0 0 0 -34 228 3

2 2 9 C4H6 + C3H6 => MCH 7.8 2 7 5 0 0 .63E-04 0 0 0 0 -311 0 0 0 -61 229
2 3 0 C4H6 + 1-C4H8 => E C H 7.4 30000 .19E-05 0 0 0 0 0-114 0 0 0 2 3 0
2 3 1 C4H6 + C4H6 => VCH 7.4 26800 .18E-05 0 0 0 0 0 0 0 0 0 2 3 1
232 CH => H2 + C H D 11.5 5 0 9 0 0 .33E-04 0 0 0 0 0 0 0 0 3 9 2 3 2 F
2 3 3 MCH => 132 + MCHD 10.5 4 9 5 0 0 .22E-04 0 0 0 0 0 0 0 0 4 8 2 3 3
2 3 4 MCH => CH4 + CHD 13.6 61100 .773-05 38 0 0 0 0 0 0 0 16 234
2 3 5 ECH => H2 + ECHD 10.5 4 9 5 0 0 .81E-06 0 0 0 0 0 0 0 0 2 2 3 5 0
2 3 6 VCH => H2 + VCHD 10.6 48400 .13E-05 0 0 0 0 0 0 0 0 1 2 3 6
237 CHD => H2 + BENZENE 12.0 4 2 5 0 0 .41E-04 0 0 0 0 0 0 0 0 5 5 2 3 7 6
2 3 8 MCHD => H2 + TOLUENE 12.5 4 3 0 0 0 .22E-04 0 0 0 0 0 0 0 0 4 8 2 3 8
2 3 9 ECHD => H2 + E-BENZENE 12.5 4 3 0 0 0 .815'-OG 0 0 0 0 0 0 0 0 2 2 3 9 '
2 4 0 VCHD = > H2 + STYRENE 12.0 43000 .13E-05 0 0 0 0 0 0 0 0 1 2 4 0
I X I T I A L CONCENTRA'T'ION I S RISED S P E C I F I C REACTION 0 ~ ~ ~ ~ * 1 102 602 01 4 9 3 1 2 1 6 3 4 7 9 1 0 0 4 2 7 2 9 - 1 1 0 9 - 1 3 9 1 1 1 9 3 2 4 1 2,

or
3

F
3

rp
W
W
494 EBERT, EDERER, AND ISBARN

the decomposition of the 3-hexyl radical and the very rapid consecutive
reactions have an analogous effect to radical chain branching reactions,
as known from oxidation processes.

Inhibition
Metathesis reactions of p radicals with propene produce a strong decrease
in the overall reaction rate. This self-inhibition occurs frequently in
hydrocarbon pyrolysis and is due to the formation of allyl radicals, which
are less reactive than the p radicals involved in the metathesis reactions.
Simulations indicate that allyl radicals have a certain reactivity and react
like ,8 radicals, because otherwise the inhibition effect would have to be
considerably stronger.

Aromatization Reactions
It is more difficult to simulate the reaction behavior at higher conversions.
Secondary product reactions become important in this region and result
in the formation of polymeric, cyclic, and aromatic compounds. Infor-
mation on the reaction paths involved in these processes is rather sparse,
if usual pyrolytic conditions are considered. This means that the cycli-
zation reactions, such as
1,3-butadiene + ethylene - cyclohexene
are not molecular reactions (Diels-Alder reactions), but proceed via dif-
ferent radical intermediates, which are not formed from butadiene exclu-
sively. There are some proposals about possible reaction paths in the lit-
erature [34],but the kinetic parameters of most of the elementary reactions
are involved are unknown. Our simulations were carried out by introducing
the corresponding molecular reactions (no. 228-no. 240) into the model and
adjusting the kinetic parameters to fit the experimental results. This is
the only feasible way a t the present time of simulating pyrolysis reactions
at high conversions. It is hoped that future investigations can specify these
reactions and describe them in terms of elementary reactions.
From the product distribution there is ample evidence that most of these
reactions will occur via addition of allyl-type radicals to alkenes and cy-
clization of the resulting radicals, followed by a hydrogen abstraction from
the cyclic species by metathetical reactions, such as

(Hydrogen elimination becomes important only at higher temperatures.)

This type of reaction explains both alkane formation and alkene con-
sumption with increasing conversion. Similar effects have been observed
 THERMAL DECOMPOSITION OF n-HEXANE 495

t [mid
Figure 9. Product formation, simulated at 750 K. l-CH4; 2-CzH6; 3-CzH4; 4-C3H*;
5-C3H6; 6-1-C4H8.

in the pyrolysis of polymeric compounds and naphtha fractions, especially

if the cracking gases are recycled to the pyrolysis reactor [35].
Therefore n-hexane is a suitable model substance for the study of py-
rolysis reactions of more complicated hydrocarbon compounds and even
of hydrocarbon mixtures.

Discussion of the Simulation

Typical results of the simulations are shown in Figures 9-11, representing
the production rate of some of the stable products as well as of a number
of the free radicals. The intervals between the points represent the step
sizes chosen by the integration routine. Because of the stiffness of the
system, the intervals are indeed very small at the beginning and are be-
coming larger during the course of the reaction. Figure 9 shows that the
alkane concentrations are continuously rising, while that of the alkenes rise
at a considerably smaller rate.
Figures 10 and 11 show the dynamics of the radical concentrations.
There is a steep increase for all free radicals in the very beginning of the
reaction, reaching the quasi-stationary conditions soon. This, of course,
does not mean that the radical concentrations remain constant. The
product inhibition effect on the overall reaction is indicated by the con-
centration profile of the H, CH3, CnH5,and l-C3H7 radicals showing rela-
tively high values in the beginning of the reaction. After the initial inhi-
bition period the CzH3 and C3H5 radicals have the highest concentrations
of all free radicals. From this point on the overall reaction follows first-
order kinetics (see section in Figure 1).
496 EBERT, EDERER, AND ISBARN

s -10
Gl
-0

-20

-30

-L -2 0 2 4
loglo t Isecl
Figure 10. Radical formation, simulated at 750 K. 1-H; 2-CH3; 3-CzH3; 4-CzH5;
5-C3H5; 6-1-C3H7; 7-2-C3H7; 8-1-methyl-allyl; 9-3-butenyl.

An interesting aspect of the simulations are the integrated reaction rates,

which are listed in Table 111. These rates are obtained by integrating the
reaction rate of each elementary reaction. They indicate how important
an elementary reaction is within a specifictype of reaction (such as initia-
tion, hydrogen abstraction). As the radical isomerization reaction l-hexyl
+ 2-hexyl has the highest integrated reaction rate, it means that it is of
greatest influence to the reaction. This also shows that the equilibrium
of the isomerization is obtained very rapidly compared with radical de-
composition. Another result is that those radical recombination reactions,
or radical chain termination reactions, in which CzH3 and C3H5 radicals
are involved, are the most important.
Another kind of importance is expressed by the sensitivities (columns
7-14, Table 111). Sensitivity characterizes the change in concentration of
a particular species due to the variation of the reaction rate constant of a
particular elementary reaction. The logarithmic or relative sensitivity si;
= b log(ci)/d log(kj)is used because this produces a better scale. A detailed
description of the method to calculate these sensitivities is given in the
Appendix. Studies of the sensitivities show that isomerization and de-
composition of the hexyl radicals have a very great influence on the product
distribution in n-hexane pyrolysis.
Furthermore the decomposition reaction of 1-butene (no. 14) has the
highest sensitivity on the consumption of n-hexane, and therefore on the
overall reaction rate. This high influence may be explained by chain
branching reactions via butene, similar to the effects discussed in connec-
tion with the pentene formation.
 THERMAL DECOMPOSITION OF n-HEXANE 497

0
b 100 200 300
t [min]
Figure 11. Product and radical formation,simulated at 750 K. l-C~H14; 2-CH4; 3-CzH4;
4-czHs; 5-H; 6-CH3; 7-2-C&3; 8-C3H5; 9-1-methyl-4-pentenyl.

An additional result of the sensitivity studies is that the initial pressure

influences the product distribution. This indicates that the reaction order
with respect to the formation of a specific product is not unity (no. 241 in
Table 111). In general the sensitivity matrix gives evidence as to how exact
the kinetic parameters of the different elementary reactions must be known
to obtain simulation results of a certain accuracy.
For special problems, that is, specific reaction conditions, the overall
reaction may be described by a simple model, consisting of a smaller number
of elementary reactions. They can be selected from the global mechanism
(Table 111)in considering the relative importance of the elementary reac-
tions indicated by the integrated reaction rates within a particular group
of elementary reactions and their sensitivity values.
A fundamental result of the simulation studies is that the establishment
of large reaction models and the adjustment of the kinetic parameters to
the experimental data by best-fit methods is only possible if no important
elementary reaction is omitted. Then models can be applied over a wide
range of reaction conditions. Also, if better and/or additional experimental
data become available, the adaptation of the model can usually not be
achieved by parameter fitting within reasonable limits, but only by adding
new elementary reactions.
The power of parameter fitting in complex models consisting of ele-
mentary reactions is widely overestimated. Parameter adjustment in order
to obtain a better fit of experimental data in models in which important
elementary reactions are missing is either not successful at all, or leads to
numerical values of the reaction constants, which can be many orders of
magnitude beyond realistic ranges.
498 EBERT, EDERER, AND ISBARN

Appendix

Sensitivity Analysis [36]

A homogeneous chemical reaction system can be described mathemati-
cally by a system of ordinary differential equations (ODES)
dc
(4) - = C = f(c,k,t)
dt
with the initial conditions c(0) = co and
c E IR; c being the concentration vector and n the number of
chemical species
k E lRp; k being the vector of reaction rate constants and p the
number of chemical equations, p 2 n
t E IRI; reaction time
and where c is dependent on c(c0,t, k [ T ( t ) ] ) .
Sensitivity s i j means the partial derivative [36-381 of the concentration
C i with respect to the rate constant kj:

This partial derivative describes the influence of a change in k j on the

concentration ci. This sensitivity is, of course, dependent on the same
variables as c. The n X p matrix S = ( s i j ) is called the sensitivity matrix.
In the inverse problem the sensitivities have an even greater importance.
Qualitatively, if s i j is a small number, then there exists only a minor in-
fluence of k, on c i , or inversely, the k , determined from measurements of
ci have a large error range. On the other hand, if sij is a large number, then
a small change of kj has a large influence on ci, or inversely, if kj is deter-
mined from measurements of c i , it has a comparatively small error range.
Differentiation of the ODE system (4) with respect to the parameters k
results in the following differential equation system:
dc - bf dc + dfc

dk dcdk dk
where dcldk is the n X p sensitivity matrix, bfldc is the n X n matrix of
the partial derivatives of the right-hand side of the ODE system (4) with
respect to the concentrations (called the Jacobian matrix J ) ,and bfldk is
the n X p matrix of the partial derivatives of the right-hand side with re-
spect to the parameters k . Graphically, this differential equation system
for the sensitivities may be represented by the following scheme:
 THERMAL DECOMPOSITION OF n-HEXANE 499

n P

representing a system of ODEs with the dimension n X p . The initial

conditions are s i j ( 0 ) = 0.

Solution Methods for the Sensitivity Differential Equations [39-411

The direct method requires the solution of eq. (6), that is, n X p ODEs,
and the solution of eq. (4), that is, n ODEs, which sums to n(P + 1) coupled
ODEs.
Another more sophisticated method is the Green's function method
+
[42-441, which requires only the solution of ( n 1)n coupled ODEs. The
differential sensitivities s i j are calculated by the direct method and the
Green's function method. There is another type of sensitivity used in the
literature, the Fourier amplitude sensitivity test (FAST) [45,46], which
produces a different measure of sensitivity, including also finite changes
in k. FAST requires more computer time than the direct method, but it
yields other, extended sensitivity information.
For numerical and practical reasons, the above-mentioned absolute
sensitivity si,; is often replaced by the relative sensitivity 5ij:

From this expression the following estimation formula, already available

in the literature [42], can be derived:

and hence,

In the thermal decomposition of n-hexane, two sorts of chemically extreme

species are involved: stable products and free radicals. If c E IR is split
500 EBERT, EDERER, AND ISBARN

into

with c1 E IRnl (free radicals) and c2 E IRn2 (stable products), and n l + n2

= n. Then eq. (4) is rewritten:
(10) C; = fl(c, k); CH = f 2 ( ~k),
Then the QSSA, which is justified by singular perturbation theory, changes
eq. (10) to:

It has been shown [14] that the evaluation of eq. (10) with a stiff solver
differs only very little from the solution of eq. (11)(in the n-hexane py-
rolysis simulation, in our temperature and pressure ranges). Equation (11)
can be calculated, for example, by a Runge-Kutta integrator for the dif-
ferential equations, and with a multidimensional Newton solver for the
algebraic equations. In our experiments on thermal decomposition of
n-hexane, only c3, which is a subset of c2, is determined. Therefore we are
only interested in the smaller sensitivity matrix dc3/dk, which is now an
n3 X p matrix.
This sensitivity matrix can be calculated by a direct method using the
QSSA. The system is solved for a basic set of ks. Then all the concen-
trations are stored and each kj is changed by 0.001%, and the system is
solved again. Because the kj are only changed a little bit, the Newton it-
erations for the algebraic equations converge very fast if the free radical
concentrations of the basic set are used as an initial guess.
This sensitivity matrix is a differential sensitivity, and this differential
sensitivity is for finite changes of kj, only a very coarse measure. Therefore
it is often only necessary to have a semiquantitative evaluation of the
sensitivity. And this can be done very easily by the following method.
First, the differential equation system is simulated up to the reaction
time of interest applying QSSA. Because up to a medium extent of con-
version the stable products (which are analyzed) are changing with time
at a nearly constant rate,

bci ( t) - A c (~t)
N-

dkj Akj
may be approximated by
 THERMAL DECOMPOSITION OF n-HEXANE 501

and hence,

If this approximation is accepted, then for the calculation of the concen-

tration of the free radicals c1, only the Newton solution of the algebraic
+
QSSA remains to be done for each k; Ak;. The rates c#z; Ak;) are +
calculated directly from the right-hand side of the differential equation.
If Akjlk; is small, convergence of the Newton iterations is attained rap-
idly.
Using this method the sensitivity matrix, which is shown partially in
Table 111, is calculated. Comparison of some entries in the sensitivity
matrix with values calculated by an exact direct method showed very good
agreement.

Acknowledgment
The authors are grateful to U. Nowak, who adapted the LARKIN
package. This work was supported by the Deutsche Forschungsgemein-
schaft.
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Received July 13,1982
Accepted November 22,1982