ISSN 00231584, Kinetics and Catalysis, 2010, Vol. 51, No. 5, pp. 635–643. © Pleiades Publishing, Ltd., 2010.

Original Russian Text © V.N. Rozanov, Yu.A. Treger, 2010, published in Kinetika i Kataliz, 2010, Vol. 51, No. 5, pp. 661–669.

Kinetics of the GasPhase Thermal Chlorination of Methane

V. N. Rozanov and Yu. A. Treger
Sintez Research and Engineering Center, Moscow, Russia
email: RozanovVN@yandex.ru
Received December 21, 2009

Abstract—Based on information concerning the rate constants of elementary steps corrected with consider
ation for experimental data obtained under laboratory, pilotplant, and industrial conditions, the kinetics of
the gasphase process of thermal chlorination of methane was considered. The form of the rate equation of
the process depends on the mode of chain termination. Of four possible variants, cross termination with the
participation of a chlorine atom and a hydrocarbon radical and quadraticlaw termination on hydrocarbon
radicals are significant under industrial conditions. The fractions of the participation of either of these vari
ants at various degrees of chlorine conversion were determined. Rate equations were found to describe the
chlorination of methane, methyl chloride, methylene chloride, and chloroform with cross and quadraticlaw
chain terminations. The overall kinetic order of these equations with respect to reactants was 1.5. Combined
equations that imply the simultaneous occurrence of cross and quadraticlaw chain terminations were pro
posed.
DOI: 10.1134/S0023158410050034

INTRODUCTION However, a comparison between the results of cal

culations performed with the use of the kinetic model
The gasphase thermal chlorination of methane by Arai et al. [3] and the data obtained in operating
has long been widely used in industry; however, only a industrial reactors, pilot plants, and laboratory setups
small number of publications devoted to the kinetics of revealed considerable differences. This inconsistence
this process are known. In an early study, Pease and stimulated us to consider this problem in more detail.
Walz [1] found that the rate of chlorine consumption
was proportional to the partial pressures of chlorine
and methane; that is, the overall reaction was of sec EXPERIMENTAL
ond order and the activation energy was 132.3 kJ/mol. A hollow lined reactor with a brick column
Under the same conditions, the rate of chlorination of arranged at the center is used in industry for chlorina
methyl chloride was higher than that of methane by a tion (this technology was developed in prewar Ger
factor of about 2, whereas, on the contrary, the rates of many). The initial cold mixture, impinging on the
chlorination of methylene chloride and chloroform central column, is heated partially from the reaction
were lower than that of methane. walls, partially as a result of mixing with a hot reaction
Much more recently, Aglulin et al. [2] also found gas, and partially by thermal emission from the brick
kinetic orders close to unity with respect to methane work. The process is performed at 480–500°С.
and chlorine in the thermal reaction of methane chlo The regime of gas motion in these reactors, which
rination. The apparent activation energy was 121.3 ± were removed from Germany as reparations after the
8.4 kJ/mol. According to Aglulin et al. [2], the rate of war, is unknown, and it cannot be described by either
methane chlorination under comparable conditions a plugflow model or a wellmixed model. It is likely
was higher by a factor of about 2 than that found earlier that this regime is close to the latter case. Therefore, to
by Arai et al. [3]. In our opinion, this discrepancy can evaluate the ratio between the rate constants of chlori
be due to the fact that Aglulin et al. [2] performed the nation of methane and methyl chloride in an industrial
study in a flowcirculation setup with a considerable reactor, we used only data on the steadystate concen
portion of the circulation loop in the light, which tration of methyl chloride in the reaction gas (under
could facilitate an additional photochemical initiation conditions of a recycle process with the complete
of the chlorination reaction. return of methyl chloride to the chlorinator). Indus
Arai et al. [3] performed the most comprehensive trial reactors operate at an excess pressure of no higher
study of the kinetics of gasphase thermal chlorination than 0.7 atm (usually, 0.5–0.6 atm) and a temperature
of not only methane but also its chlorinated deriva of 480–500°С.
tives. They proposed a rate equation for the process, in At many plants for the manufacture of chlo
which orders with respect to chlorine and methane (or romethanes, in particular, in Russia, the recycle of
corresponding chloromethanes) were equal to unity. methyl chloride is used and only methylene chloride

635
636 ROZANOV, TREGER

Table 1. Composition of the chloromethanes obtained upon potassium iodide to absorb chlorine and hydrogen
methane chlorination chloride (~100 mm of water).
Composition of chloromethanes, wt % The laboratory experiments on methane chlorina
Tempera tion in a hollow volume were performed in two types of
ture, °С CH3Cl CH2Cl2 CHCl3 CCl4 reactors. A reactor close to the model of a plugflow
apparatus was 20 mm in diameter and 150 mm in
Laboratory data obtained in this work (CH4 : Cl2 = 5) length; a thermocouple 7 mm in diameter was
380 82.00 15.95 2.00 0.05 arranged within the reactor. A reactor close to the
420 74.10 21.06 4.58 0.26 model of a wellmixed apparatus was 80 mm in diam
460 68.06 24.50 6.88 0.56 eter and 50 mm in height; a stirrer was placed within it.
The reactors were heated with an external electric
500 66.32 25.21 7.58 0.89 heating unit.
Calculation from published data [3] (CH4 : Cl2 = 1) The ethane content of methane was no higher than
380 52.70 36.85 9.86 0.59 0.01 vol %, and the methane purity was no less than
420 61.35 32.51 5.85 0.29 99.88%. The impurity of oxygen in chlorine was no
higher than 0.005%, and the purity of chlorine was no
460 68.44 27.87 3.55 0.14 less than 99.7%.
500 74.08 23.66 2.19 0.07 The gas chromatographic analyses of the reaction
mixture in laboratory, pilot, and industrial setups were
performed after washing the reaction mixture in
and chloroform are separated as commercial products. Drexel bottles filled with a solution of potassium
Methyl chloride is returned to the reactor simulta iodide to remove chlorine and hydrogen chloride and
neously with the return of excess methane, which is drying with calcium chloride. Triphenyl phosphate on
required for explosionproof operation and heat Sferokhrom was used as a stationary phase; the col
removal from the reaction occurring in a hollow adia umn length was 6 m, and the column temperature was
batic reactor. The conversion of methane is about 100°С. The contents of Drexel bottles were titrated
15%, and the conversion of chlorine is 99.9% or with a solution of sodium thiosulfate to determine the
higher. amount of unreacted chlorine and then with an alkali
The pilot reactor with internal recycle is a mixing solution to determine the amount of released hydro
apparatus 800 mm in diameter and 3 m in cylindrical gen chloride.
part height [4]. A cold starting mixture is introduced
into the reactor at a high rate through a nozzle.
Because of this, conditions for the injection of two to RESULTS AND DISCUSSION
four volumes of hot reaction gas are generated. After The reliability of experimental and calculated data
mixing in a tube arranged at the center of the reactor, was checked using several tests. First, this is the rate of
the temperature of the mixed flow reaches the temper the process on which the reactor volume required for
ature of the onset of reaction and almost the entire reaching a specified value of xCl depends. The rate of
chlorination process occurs in the ring space between reaction calculated from published data [3] was found
the central tube and reactor walls. Chlorine does overestimated, especially, in experiments performed at
almost not participate in the internal recycle because it a pilot plant under pressure. This can be due to the fact
almost completely reacts in the ring space. that the overall order of reaction with respect to start
We used data obtained in the pilot reactor to evalu ing reactants, which was taken by Arai et al. [3], is 2,
ate the accuracy of calculation results at high degrees whereas the overall order of reaction is 1.5 in three
of chlorine conversion (xCl) and to estimate the effect other alternative kinetic schemes (see below).
of pressure on xCl. The reaction was performed in the Another difference of data published by Arai et al.
pilot reactor at an excess pressure of no higher than [3] from our experimental results is a higher (by a fac
1.5 atm. Circulation gas from an operating facility or, tor of ~2) yield of methyl chloride and lower (also by a
sometimes, methane was mainly supplied for chlori factor of ~2) yields of chloroform and carbon tetra
nation. The temperature was maintained within a chloride. Moreover, according to activation energies
range of 400–420°С. These parameters, as well as the found by Arai et al. [3], the yields of chloroform and
rate of supply and the composition of starting reac CCl4 would increase with temperature, whereas they
tants, in the pilot and industrial plants differed only monotonically increased in accordance with our labo
slightly, if any. ratory data (Table 1).
The main kinetic data on the effects of tempera The calculation performed under the same condi
ture, contact time, and initial reactant concentrations tions (the molar ratio CH4 : Cl2 = 5) based on kinetic
on the rate of reaction were obtained in laboratory data [3] afforded the yield of CCl4 lower than 0.01%
reactors. The reactor pressure was somewhat higher even at 350°С. For clarity, we calculated xCl at CH4 :
than atmospheric pressure because of the resistance Cl2 = 1, when the yields of chloroform and CCl4
produced by Drexel bottles filled with a solution of became considerable (Table 1). We did not perform

KINETICS AND CATALYSIS Vol. 51 No. 5 2010

 KINETICS OF THE GASPHASE THERMAL CHLORINATION OF METHANE 637

experiments at this ratio in a hollow reactor because an Having data on the reaction kinetics of elementary
explosive mixture is formed in this case. steps in the radical chain chlorination of methane and
using the method of steadystate concentrations, we
Another adequacy test for the kinetic model of the
can calculate the kinetics of the overall process [6]:
methane chlorination process is the concentration of
methyl chloride in the reaction gas under recycling
conditions. The concentrations of methyl chloride in Chain initiation
circulation and reaction gases varied from 10 to
Cl 2 ⎯⎯ → Cl + Cl .
k1 • •
17 mol % depending on CH3Cl losses. At the same (1)
time, the calculation of the process with methyl chlo
ride recycling based on kinetic data [3] gives 42% at a Chain propagation
temperature of 350°С; this value suggests the inade
Cl• + RH ⎯⎯→ HCl + R•;
quacy of the kinetic scheme [3]. k
(2) 2

Finally, the last test, which seems theoretically k

important but is actually of great practical use, is the
(3) R• + Cl 2 ⎯⎯
3
→RCl + Cl•.
character of chain termination. The fact of the matter
is that chlorinated С2 hydrocarbon impurities, which Chain termination
make the target products (commercial chlo
Cl + Cl + M ⎯⎯→ Cl 2 + M ,
• • k
romethanes) difficult to separate, are formed upon (4) 4

quadraticlaw termination. k
R + R ⎯⎯→ R − R,
• •
(5) 5

The boiling temperatures of such impurities are k

close to the boiling temperature of a chlorinated (6) R• + Cl• ⎯⎯
6
→ RCl ,
methane derivative (for example, cf. Tb of 1,1dichlo
roethane and cis1,2dichloroethylene with Tb of (7) C l• + w a ll ⎯k⎯ 7
→ C l ads .
chloroform); other impurities form azeotropic mix Different rate equations can correspond to the
tures boiling close to the main component (1,2 reaction scheme depending on the predominance of a
dichloroethane with CCl4 or, according to our data, particular termination reaction. The orders of these
1,1dichloroethane with chloroform). In this case, it reactions with respect to chlorine or methane varied
should be borne in mind that requirements imposed from 0.5 to 1.5 or from 0 to 1, respectively [6]:
on the concentrations of individual impurities are
rigid: the concentrations of 1,1dichloroethane in w4 = k2 k1/ k4 pCH 4 p 0.5
Cl 2,
chloroform and 1,2dichloroethane in carbon tetra
chloride should be no higher than 0.002%. To remove w5 = k3 k1/ k5 pCl
1.5
2
,
the above impurities from chloromethanes, the pro w6 = k1k2k3/ k6 pCH
0.5
p ,
4 Cl 2
cess is usually performed in a batch mode; this results
in product losses, additional consumption of materials w7 = ( k1k2/ k7) pCH4 pCl 2,
and other resources, and the formation of a large were k1–k7 are the rate constants of corresponding
amount of wastes. For the purification of methylene
chloride, it was proposed to treat it with a solution of steps 1–7, and pCH4 and pCl 2 are the partial pressures of
potassium permanganate. In industry, pure and dry methane and chlorine, respectively.
chloroform (separated by rectification) containing The direct recombination of chlorine radicals is
only 0.03% 1,1dichloroethane is stirred with oleum improbable because the recombination energy is suffi
for 6 h; then, it is neutralized with a solution of sodium cient for the decomposition of the resulting chlorine
hydroxide and subjected to azeotropic drying on a rec molecule into atoms. The probability of the reaction of
tification column with 100 plates. quadraticlaw chain termination on chlorine radicals
with energy transfer to inert particle M is also low
However, this subject matter should be considered because it implies the simultaneous collision of three
individually; here, we will select an area directly con particles.
cerning the subject matter of this work. Preliminary
According to Emanuel’ and Knorre [7], the con
results suggested that it is desirable to exclude qua
centration of chlorine atoms should be higher than the
draticlaw chain termination on hydrocarbon radicals.
concentration of hydrocarbon radicals R• by a factor
The reaction mechanism of chain termination on a of about 104 in order that the rate of recombination on
wall corresponds to the first orders of reaction with chlorine radicals with inert particle M may be com
respect to chlorine and methane. The use of a rela mensurable with the rate of cross termination or ter
tively long (60 cm) and narrow (2 cm in diameter) mination on hydrocarbon radicals. At elevated pres
reactor by Arai et al. [3] and a low process temperature sures, a certain contribution from quadraticlaw ter
(275–370°С), at which chain initiation could mainly mination on chlorine radicals should be taken into
occur on a wall [5], could be favorable for this mecha account because of an increase in the rate of trimolec
nism. ular reaction of chlorine radicals with particle M.

KINETICS AND CATALYSIS Vol. 51 No. 5 2010

638 ROZANOV, TREGER

The reactions of cross termination and quadratic Thereafter, we intended to derive a single rate equation
law termination on hydrocarbon radicals can occur for the reaction of methane chlorination and to evalu
because the energy released in this case is distributed ate the contributions of either of these possible com
over many bonds to protect the resulting molecule ponents to the overall process.
from decomposition for a time. Within this time inter
Table 2 summarizes the Arrhenius equation param
val, this molecule manages to collide with another eters for the elementary steps of methane chlorina
molecule and to transfer a portion of its excess energy
tion, which were mainly taken from publications con
to it. It was reliably established that the recombination
• cerning more or less comprehensive studies of this
reaction of methyl radicals 2 C H3 → C2H6 occurs at process. The parameters used in the calculations are
each binary collision [8]. boldfaced.
Thus, there are two other ways for excluding or The numerical values of the constant k1 were
decreasing the formation of chlorinated С2 hydrocar mainly measured by various authors in the region of
bon impurities: first, to exclude quadraticlaw termi low pressures, and they belong to a bimolecular reac
nation on hydrocarbon radicals by generating condi tion (dimensionality of cm3 mol–1 s–1). We managed to
tions for termination on the wall and, second, to determine the constant k1 with the dimensionality
increase the chain length.
of s–1 (because of this, the rate constants of chain ter
Decreasing temperature in order to increase the mination acquired a correct dimensionality of
chain length, we managed to decrease the formation of
impurities; however, this decrease was insufficient [9]; cm1.5 mol–0.5 s–1) using the rate constant k–1 of the
in addition, the rate of the main process decreased at a reverse reaction measured in the region of high pres
lower temperature. sures [15] and the equilibrium constant found from
1
The chlorination of methane in a flow reactor with thermodynamic data [16].
out and with filling the reactor volume with glass rings
for increasing the wall surface area [10] did not change The rate constants of the chlorination reactions of
both quantitative and qualitative compositions of the methane, methyl chloride, methylene chloride, and
resulting chlorinated С2 hydrocarbon byproducts. It chloroform at temperatures of 623, 653, 683, 713, 743,
is likely that chains in the test process were insuffi and 773 K were calculated from equations corre
ciently long. sponding to cross (kc) and quadraticlaw (kq) chain
termination. As applied to the chlorination of meth
Taking into account these data, we can exclude the ane, methyl chloride, methylene chloride, and chlo
possibility of chain termination on the wall in the roform, these equations have the following forms,
course of the methane chlorination reaction in a hol respectively (constant numbers are specified in
low volume, the more so because the surface area to Table 2):
volume ratio (S/V) in an industrial reactor is much
smaller than that in a laboratory reactor. De Bernardez
k1k2k3 k1
and Cassano [11] also made a conclusion that the con kcCH 4 = and kqCH4 = k3 ;
tribution of termination on the wall is insignificant. k11 k15
Consequently, it is believed that only cross and
quadraticlaw (on hydrocarbon radicals) chain termi k1k4k5 k1
kcCH3Cl = and kqCH3Cl = k5 ;
nation play the most important role in the bulk ther k12 k19
mal chlorination of methane. The cross termination
makes a considerable contribution to the course of the k1k6k7 k1
process with methylene chloride recycling, when a kcCH 2Cl 2 = and kqCH2Cl 2 = k7 ;
steadystate concentration of CH3Cl results from k13 k22
competition between the reactions of its formation
k1k8k9 k1
upon methane chlorination and consumption in the kcCHCl 3 = and kqCHCl 3 = k9 .
subsequent chlorination. The fact is that the rate of the k14 k24
process with quadraticlaw termination on hydrocar
bon radicals depends only on the concentration of Next, the resulting constants were corrected to
chlorine rather than on the concentrations of methane obtain the most reliable description of experimental
and methyl chloride, whereas it is proportional to the data. Table 3 summarizes the calculated rate constants
concentrations of methane and methyl chloride to a of methane, methyl chloride, methylene chloride, and
power of 0.5. chloroform chlorination and the rate constants cor
Thus, it seemed reasonable to calculate the rate of rected with consideration for experimental data and
methane chlorination on cross and quadraticlaw converted into the dimensionality of l0.5 mol–0.5 s–1.
chain termination on hydrocarbon radicals using the From these data, we calculated Arrhenius equation
published rate constants of elementary steps and then 1 Data required for the calculation were provided by Yu.A. Kol
to correct the results with consideration for experi banovskii and N.N. Buravtsev (Institute of Petrochemical Syn
mental laboratory, pilot, and industrialscale data. thesis, Russian Academy of Sciences).

KINETICS AND CATALYSIS Vol. 51 No. 5 2010

 KINETICS OF THE GASPHASE THERMAL CHLORINATION OF METHANE 639

Table 2. Arrhenius equation parameters for the elementary steps of the radical chain process of methane chlorination (based on
published data)
log A Activation energy,
Step no. Step A, cm3 mol–1 s–1 References
[cm3 mol–1 s–1] kcal/mol
1
. . 2.32 × 1013 13.37 ± 0.18 46.96 ± 5.72 [12]
Cl2 + M Cl + Cl + M
1.1 × 1014
– 46.99 [13]
– 15.93 55.9 [14]
(5.7 ± 1) × 1014* – 56.67 [15, 16]
2
. . (5.75 ± 2.78) × 1012 – 2.68 ± 0.5 [17]
Cl + CH4 C H3 + HCl
(2.22 ± 0.97) × 10 12
– 2.524 ± 0.126 [18]
– 13.7 3.85 [19]
– 13.5 3.3 [20]
3
. . – 12.9 2.3 [19]
C H3 + Cl2 CH3Cl + Cl
– 13.5 2.42 [21]
(2.88 ± 1.06) × 1012 – 0.48 ± 0.2 [22]
1.07 × 1013 – 2.15 [23]
4
. – 13.5 3.1 [19]
Cl + CH3Cl C H2Cl + HCl
(1.95 ± 0.40) × 1013 – 2.48 ± 0.5 [17]
(1.08 ± 0.24) × 1013 – 2.2 ± 0.16 [24]
– 14.2 2.95 [21]
5
. . (9.12 ± 1.01) × 1011 – 0.98 ± 0.2 [25]
C H2Cl + Cl2 CH2Cl2 + Cl
– 12.0 2.93 [21]
– 12.6 3.0 [19]
6
. . (1.86 ± 0.69) × 1013 – 2.68 ± 1.0 [17]
Cl + CH2Cl2 C HCl2 + HCl
– 13.4 3.1 [19]
– 13.41 ± 0.07 2.96 ± 0.1 [26]
7
. . (5.13 ± 2.79) × 1011 – 2.46 ± 1.0 [25]
C HCl2 + Cl2 CHCl3 + Cl
– 12.0 4.0 [19]
– 12.3 4.15 [21]
8
. . (6.64 ± 3.0) × 1012 – 2.92 ± 0.5 [27]
Cl + CHCl3 C Cl3 + HCl
– 12.84 ± 0.04 3.32 ± 0.09 [26]
– 13.2 3.3 [19]
9
. . (4.42 ± 4.0) × 1011 – 4.73 ± 1.0 [28]
C Cl3 + Cl2 CCl4 + Cl
– 11.74 5.0 [26]
– 12.3 6.0 [21]
– 12.86 5.3 [20]
10
. . – 14.35 ± 0.15** –1.8 ± 0.44 [14]
Cl + Cl + M Cl2 + M
– 15.1** –1.6 [29]
(4 ± 1) × 1013 – 0 [13]
11
. . – 13.64 ± 0.2 0 [30]
Cl + C H3 CH3Cl
– 13.9 0 [21]
– 14.6 0 [11]
12
. . – 13.7 0 [21]
Cl + C H2Cl CH2Cl2
– 14.4 0 [11]

KINETICS AND CATALYSIS Vol. 51 No. 5 2010

640 ROZANOV, TREGER

Table 2. (Contd.)
log A Activation energy,
Step no. Step A, cm3 mol–1 s–1 References
[cm3 mol–1 s–1] kcal/mol
13
. . – 13.7 0 [21]
Cl + C HCl2 CHCl3
– 14.35 0 [11]
14
. . – 13.7 0 [21]
Cl + C Cl3 CCl4
– 14.4 0 [11]
15
. . – 13.5 0 [26]
C H3 + C H3 C2H6
– 13.7 0 [30]
16
. . – 13.1 0 [11]
C H3 + C H2Cl C2H5Cl
17
. . – 13.1 0 [11]
C H3 + C HCl2 C2H4Cl2
18
. . – 13.0 0 [11]
C H3 + C Cl3 C2H3Cl3
19
. . – 12.6 0 [26]
C H2Cl + C H2Cl C2H4Cl2
– 12.6 0 [11]
20
. . – 12.5 0 [11]
C H2Cl + C HCl2 C2H3Cl3
21
. . – 12.3 0 [11]
C H2Cl + C Cl3 C2H2Cl4
22
. . – 12.4 0 [26]
C HCl2 + C HCl2 C2H2Cl4
– 12.4 0 [11]
23
. . – 12.1 0 [11]
C HCl2 + C Cl3 C2HCl5
24
. . – 11.8 – [19]
C Cl3 + C Cl3 C2Cl6
– 12.66 – [26]
– 13.9 – [26]

* A in units of s–1. The value was obtained by multiplying the equilibrium constant of step 1 K1 = 101.23 exp ⎛ – ⎞ from [15] by the rate con
56.67
⎝ RT ⎠
stant of the reverse reaction k–1 = (4 ± 1) × 1013 cm3 mol–1 s–1 from [16].
** A in units of cm6 mol–2 s–1.

parameters for the reactions of methane, methyl chlo equation wqRH = kqRH [Cl 2]
1.5
with quadraticlaw termi
ride, methylene chloride, and chloroform chlorina 2
tion with cross and quadraticlaw chain terminations ⎛ k RH ⎞
on hydrocarbon radicals. nation at ⎜ cRH ⎟ [RH] Ⰷ 1.
⎝ kq ⎠ [Cl 2]
We also propose the combined equation The rate equations for the chlorination of methane
and chloromethanes (in mol l–1 s–1) can be repre
RH
kc sented in the following form (activation energies in
=
RH 0.5
w 0.5 [RH] [Cl 2]. J/mol are specified):
⎧⎪⎛ k RH ⎞ [RH] ⎫⎪
2

⎨⎜ cRH ⎟ + 1⎬
⎩⎪⎝ kq ⎠
[Cl 2] ⎪
⎭ Methane
= kc 4[ CH 4] [ Cl 2]
CH 4 CH 0.5
wc

( )
2
⎛ k RH ⎞
[RH] Ⰶ 1, it is transformed into the equa 129 000
= 2.31 × 10 exp −
11 0.5
At ⎜ cRH ⎟ [CH 4] [ Cl 2];
⎝ kq ⎠ [Cl 2] RT
tion wcRH = kcRH[ RH]0.5[ Cl 2], which corresponds to
cross termination, whereas it is transformed into the
wqCH4 = kqCH4[Cl 2]1.5 = 1.32 × 1012exp − ( 128RT900)[Cl ] ;
2
1.5

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 KINETICS OF THE GASPHASE THERMAL CHLORINATION OF METHANE 641

Table 3. Calculated and experimental rate constants of the chlorination reactions of methane, methyl chloride, methylene chlo
ride, and chloroform in l0.5 mol–0.5 s–1

Tempera CH4 CH3Cl CH2Cl2 CHCl3

ture, K calculated experimental calculated experimental calculated experimental calculated experimental
. .
Cross termination R + Cl RCl (wc = [RH]0.5[Cl2])
623 5.89 3.38 5.63 5.63 2.51 3.13 0.391 0.598
653 18.4 10.6 17.8 17.8 8.13 10.1 1.30 1.98
683 52.2 29.8 50.9 50.9 23.8 29.6 3.92 5.97
713 137 78.2 133 133 64.5 80.1 10.6 16.2
743 327 188 323 323 160 199 26.7 40.6
773 744 426 733 733 372 462 62.6 95.2
. .
Quadraticlaw termination R + R R–R (wq = kq[Cl2]1.5)
623 20.2 20.2 16.4 17.9 4.02 5.80 0.417 0.656
653 63.3 63.3 52.5 57.3 13.5 19.5 1.41 2.22
683 177 177 150 164 40.5 58.5 4.33 6.80
713 458 458 398 435 112 162 12.1 19.0
743 1100 1100 977 1070 281 406 31.1 49.0
773 2490 2490 2210 2410 667 964 74.0 115

CH 4 CH 2Cl 2
kc kc
= =
CH4 0.5 CH Cl
2 2 0.5
woverall 0.5 [CH 4] [Cl 2]. woverall 0.5 [ CH 2Cl 2] [ Cl 2].
⎧⎪⎛ k CH4 ⎞ [CH ] ⎫⎪
2
⎧⎪⎛ k CH2Cl 2 ⎞ [CH Cl ] ⎫⎪
2
4 +1 2 +1
⎨⎜ cCH4 ⎟ ⎬ ⎨⎜ cCH2Cl 2 ⎟ 2
⎬
⎪⎩⎝ q ⎠
k [Cl 2] ⎪⎭ ⎪⎩⎝ q
k ⎠ [Cl 2] ⎪⎭

Methyl Chloride Chloroform

= kc = kc
CH 3Cl CH 3Cl 0.5 CHCl 3 CHCl 3 0.5
wc [ CH 3Cl] [Cl 2] wc [ CHCl 3] [ Cl 2]
= 5.37 × 10 exp −
11 130900
RT ( 0.5
[CH 3Cl] [ Cl 2]; ) = 1.56 × 10 exp −
11 136100
RT ( 0.5
[CHCl 3] [ Cl 2]; )
= kq
CHCl 3 CHCl 3 1.5
wqCH3Cl = kqCH3Cl[ Cl 2]1.5 wq [ Cl 2]

= 2.09 × 1012exp −
131900
RT (
[Cl 2]1.5; ) = 2.94 × 1011exp −
138 900
RT ( [ Cl 2]1.5; )
CH3Cl CHCl 3
kc kc
woverall3 =
CHCl 0.5
=
CH Cl 0.5
0.5 [ CHCl 3] [ Cl 2].
3
woverall 0.5 [ CH 3Cl] [ Cl 2].
⎧⎪⎛ k CH3Cl ⎞ [CH Cl] ⎫⎪
2
⎧⎪⎛ k CHCl 3 ⎞ [CHCl ] ⎫⎪
2

⎨⎜ cCH3Cl ⎟ 3
+ 1⎬ ⎨⎜ cCHCl 3 ⎟ 3
+ 1⎬
⎩⎪⎝ ⎠ [Cl ]
⎩⎪⎝ q ⎠
k [Cl 2] k ⎪⎭
⎭⎪ q 2

To compare the rates of elementary steps of cross

Methylene Chloride and quadraticlaw terminations on hydrocarbon radi
cals (using the step of methane chlorination as an
= kc
CH 2Cl 2 CH 2Cl 2 0.5 example), we can consider the corresponding con
wc [ CH 2Cl 2] [ Cl 2]

( )
stants of elementary steps specified in Table 2:
133 700
= 5.14 × 10 exp −
11 0.5
[CH 2Cl 2] [ Cl 2];
RT wq  3]2
k15 [ CH
=
 3][ Cl i]
w c k11[ CH
wqCH2Cl 2 = kqCH2Cl 2[ Cl 2]1.5

( )
13   3]
136 200 3.16 × 10 [ CH 3] [CH
= 1.57 × 1012exp − [ Cl 2]1.5; = i = 0.723 .
4.37 × 10 [ Cl ] [Cl i]
13
RT
KINETICS AND CATALYSIS Vol. 51 No. 5 2010
642 ROZANOV, TREGER

xCl, % a result of recombination of hydrocarbon and chloro

100 hydrocarbon radicals in the bulk thermal chlorination
of methane cannot be avoided.
Thus, in this work, we found rate equations for the
80 reactions of methane, methyl chloride, methylene
chloride, and chloroform chlorination using a calcula
tion technique with consideration for experimental
1 2
60 data; these reactions occur with cross and quadratic
law chain termination. We also proposed combined
equations that imply simultaneous cross and qua
40 draticlaw chain terminations. The overall kinetic
order of these equations with respect to reactants is
1.5, whereas it should be 2 in accordance with pub
20
lished data. This especially strongly affects the sizes of
reactors for methane chlorination at a pressure of
10 atm, the design of which was the subject matter of
our studies.
0 20 40 60 80 100
Fraction of quadraticlaw termination, %
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