Res Chem Intermed (2012) 38:1133–1147

DOI 10.1007/s11164-011-0449-x

Autocatalytic gas-phase dehydrogenation of ethane

Valerii N. Snytnikov • Tatyana I. Mishchenko •

Vladimir N. Snytnikov • Sergei E. Malykhin •

Vasilii I. Avdeev • Valentin N. Parmon

Received: 6 October 2011 / Accepted: 28 November 2011 / Published online: 16 December 2011
Ó Springer Science+Business Media B.V. 2011

Abstract Homogeneous gas-phase pyrolysis of ethane by continuous CO2 laser

irradiation was used in our experiments for bulk heating of the reaction mixture.
Laser energy was absorbed by ethylene, the main product of ethane dehydrogenation,
and transferred to the reaction medium via collisional relaxation. A mechanism of
ethane dehydrogenation is suggested to describe the pyrolysis process. The mecha-
nism is autocatalytic in respect of ethylene and includes ethane–ethylene interaction
with the formation of methyl and propyl radicals. Rate constants of elementary
reactions, selectivity, and yields of pyrolysis products were determined. The com-
position of ethane dehydrogenation products determined in the experiments was
substantially different from the calculated thermodynamic equilibrium composition.

Keywords Ethane pyrolysis  Autocatalysis  Laser irradiation  Ethylene biradical

Introduction

Dehydrogenation of ethane yielding ethylene as a basis of current large-scale

processes has been studied intensively since the 1930s [1–3]. The radical-chain
mechanism for ethane pyrolysis developed at that time is now widely accepted
[4, 5]. The scheme for ethane dehydrogenation includes a radical-generation step:
C2 H6 ! CH3  þ CH3  ð1Þ
and chain growth and radical decay steps occur with the formation of C4H10.
However, simulation based on such schemes cannot describe the process of ethane
pyrolysis occurring with high conversion at atmospheric pressure.

V. N. Snytnikov  T. I. Mishchenko  V. N. Snytnikov 

S. E. Malykhin (&)  V. I. Avdeev  V. N. Parmon
Boreskov Institute of Catalysis, Lavrentieva 5, Novosibirsk, Russian Federation 630090
e-mail: malykhin@catalysis.ru

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1134 V. N. Snytnikov et al.

To fit the experimental data a variety of kinetic schemes have been suggested;
these were often based on semiempirical models developed ad hoc, for example [6].
These schemes were also extended for simulation of the pyrolysis of heavier
hydrocarbons. This led to the development of more complicated schemes of ethane
thermal decomposition which include a much larger number of reactions than in the
mechanism mentioned above. These schemes are treated with extensive use of
numerical methods [7–10].
In the works listed, the endothermic reaction of ethane decomposition is regarded
as a gas-phase process. However, in the experiments the energy for the reaction is
commonly supplied via the reaction vessel walls. Thus, heterogeneous processes
taking place on the hot wall surfaces lead not only to the formation of free radicals,
but also to their decay.
The main products of the homogeneous–heterogeneous process of equilibrium
thermal pyrolysis of ethane are C2H4, CH4, and H2; small amounts of C2H2, C3H6,
C4H10 and other compounds are also produced. Acetylene and propylene are involved
in the formation of cyclic and aromatic compounds followed by coke formation on the
surface of reaction vessels [11]. The composition of the product depends on the wall
material and other reaction conditions.
To achieve high temperatures for ethane pyrolysis, microwave irradiation [12] or
electron beams [13] are used. In that case, kinetic schemes and reaction products of
plasma-chemical technology differ from conventional thermal processes of
pyrolysis. In non-equilibrium plasma-chemical processes the products may include
graphite [14], acetylene [15, 16], or more heavy condensation products [17].
Thermodynamic calculations are used to estimate the product composition [18].
Study of the pyrolysis of light hydrocarbons, including ethane, has been reported
in many papers. Experimental measurement [19] and numerical simulation data [20]
concentrated mainly on the route of formation of intermediates [21–26], and the
distribution of final products [27]. Interaction of hydrocarbons with catalysts has
also been studied [28–30].
Of great interest is ethane dehydrogenation under homogeneous conditions in the
absence of heterogeneous reactions on the walls. Snytnikov et al. [31] performed
homogeneous gas-phase decomposition of ethane in the absence of walls at
atmospheric pressure without an inert diluent. Butane was not found in the reaction
products; the main products were C2H4, CH4, and H2. Homogeneous conditions
were provided by heating the reaction mixture by IR laser irradiation, with the
energy supplied directly to the gas. Conversion of laser energy into heat energy
occurred with the use of ethylene, which was among the main reaction products.
The radiative energy absorbed by ethylene was transferred, on collisional relaxation,
to the reaction medium, leading to its local heating. This was a thermal process
without generation of excited electronic states in the molecules. The results obtained
were interpreted as a radical-chain mechanism of gas-phase pyrolysis of ethane
which was autocatalytic in nature in respect of ethylene at C2H4 concentrations
above 5%.
The objectives of the work discussed in this paper were to derive a kinetic
scheme for gas-phase pyrolysis of ethane for the main observable products,
including the steps of acetylene and propylene synthesis, and to determine the

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Autocatalytic gas-phase dehydrogenation of ethane 1135

selectivity and yield of ethylene and other reaction products at moderate

temperatures before plasma formation.

Experimental setup for studying ethane pyrolysis

A flow chart of the experimental setup for studying the gas-phase reactions under
homogeneous conditions is presented in Fig. 1. Radiation from a continuous-wave
CO2 laser of wavelength k & 10.6 lm and maximum radiation power W = 130 W
was used as energy source for the endothermic processes. The reactor was a 6 cm3
cylindrical quartz cell of inner diameter D = 16 mm and length L = 30 mm.
Radiation was supplied to the reactor volume through a window of an antireflection
plane–parallel ZnSe plate (4). Plate 5, of GaAs with a reflection factor of ca. 70% at the
wavelength k & 10.6 lm, was mounted at the reactor outlet. This allowed us to
enhance the uniformity of radiation absorption along the cell and to measure the
energy absorbed in the volume. Radiation power was measured with separating plates
of ZnSe using an LM-2 standard instrument (Germany) with a time resolution of 2.5 s.
To measure radiation energy at the reactor outlet, calorimeter 7 based on a
thermoresistor sensor with a power integration time no shorter than 1 min was used.
The absorption coefficient of ethylene in the reactor was estimated as a & 3.6 9
10-3 cm-1 Torr-1 (or a & 10-19 cm-2 at T = 300 K).
The reactor has three stopcocks. One of these, which was closed with a silicone
stopper, was used to take samples for chromatographic analysis. The other two
enabled us to replace the gas mixture in the reactor. The laser irradiation time of the
mixture was varied from 1 to 20 s (to within ± 0.1 s). When the pressure in the
chamber exceeded 1 bar, excess gas was released to the atmosphere, ensuring
the absence of backward flow of atmospheric gas into the chamber. Chromato-
graphic analysis of gas samples was performed before and after irradiation.

Fig. 1 Setup for studying thermal gas-phase pyrolysis of ethane: 1 reactor, 2 CO2 laser, 3 optical train
mirrors, 4 optical window of ZnSe, 5 semitransparent window of GaAs, 6 LM-2 radiation power meter,
7 radiation energy meter, 8 chromatographs, 9 gas-flow controller

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1136 V. N. Snytnikov et al.

The reactor thermal fields were established within 0.2 s. The gas temperature was
estimated using methods described elsewhere [31, 32]. The temperature in the near-
surface gas layer with a thickness of approximately 2 mm quickly dropped to
350–380 K.

Quantum-chemical simulation

For most of the reactions considered in this work experimental data are available
[31, 33]. However, some possibilities cannot be verified by use of these existing
experimental data, for example some routes of generation of methyl radicals, etc. To
this end, quantum-chemical simulations were used to estimate missing kinetic
scheme data. These reactions were probed in quantum-chemical simulation by the
synchronous transit-guided Quasi-Newton method [34] (abbreviated as QST3 in
Gaussian 09). The QST3 method requires three points on the reaction route to be
defined: a reactant, a product, and an estimated structure for the transition state.
Optimum geometries were found for all these structures, and vibrational analysis
was performed to ensure the structure is a proper minimum and to account for the
zero-point energy.
Spin-unrestricted double-hybrid density functional theory B2PLYP [35] with
standard triple-zeta 6-311g(d,p) basis set [36] was applied throughout. All calcula-
tions were performed within the Gaussian 09 quantum-chemical package [37].
The chosen level of theory was validated by the experimental data. For example,
the energy barrier for hindered ethylene rotation along the C=C bond is 272 kJ/mol
[38]. The former reaction barrier was estimated as 253 kJ/mol. The activation
energy for ethane decomposition to methyl radicals is 360 kJ/mol [33], whereas the
calculated activation energy is 356 kJ/mol. Therefore, the b2plyp/6-311g(d,p)
method seems to be adequate for the purpose of this work.

Results and discussion

Ethane pyrolysis

The effect of laser irradiation power, the fraction of ethylene in the initial mixture,
and exposure time of the reaction mixture on ethane pyrolysis was studied
experimentally. The main products of pyrolysis were C2H4, CH4 and H2. C2H2 and
C3H6, which are always present in the reaction products, accounted for less than 1.8
and 0.6 vol.%, respectively. Other products, for example butane, butylene, benzene,
toluene, etc., which are typical of pyrolysis under homogeneous–heterogeneous
conditions, were not found chromatographically.
The dependence of ethane conversion on laser irradiation power is presented in
Fig. 2 for the initial ethane–ethylene mixture with the ethylene content 18 vol.%
and exposure time 5.5 s. Ethane conversion increased from 3 to 80% as the laser
irradiation power rose from 40 to 91 W, with ethane conversion not exceeding 10%
at powers up to 44 W. When the power of laser irradiation reached 73 W, ethane

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Autocatalytic gas-phase dehydrogenation of ethane 1137

Fig. 2 Ethane conversion (for an exposure time of 5.5 s) versus laser irradiation power (left) and
exposure time (right). Composition of the initial ethane–ethylene mixture: black dots C2H6—82 vol.%,
C2H4—18 vol.%; open dots C2H6—91 vol.%, C2H4—9 vol.%

conversion reached a maximum (ca. 80%), and further increase of the power had no
significant effect on ethane conversion. The points for the initial mixture with 9
vol.% ethylene content are shown in the same plot. The 10% value of ethane
conversion shifted to the 70-W region of laser irradiation power. At 83 W, 74%
conversion was achieved. Thus, for the initial mixture with a low ethylene content,
initiation of ethane conversion shifted to the region with higher power.
The experimental procedure was conducted without thermal insulation of the
reactor walls, so heat losses to the environment occurred. This changed the time to
establish heat fields in the reactor volume, which is closely related to the fraction of
the sensitizer in the reaction zone: the lower the amount of ethylene, the higher is
the laser energy needed to heat the reaction mixture to a specified temperature.
Detailed estimates of the reactor thermophysics are reported elsewhere [31, 32].
The dependence of ethane conversion on exposure time for the initial mixture
with 9 vol.% ethylene content at 73 W is presented in Fig. 2. For exposure times of
2.4–3 s the ethane conversion did not exceed 9%. It then rose to 70% as the
exposure time of reaction mixture increased to 6.5 s, and further attained a
maximum value of 82%.
The experimental data obtained were used to calculate the selectivity (S) and
yield (Y) of the carbon-containing reaction products. The selectivity and yield were
found by use of the formulas:
ni  N  100%
Si ð%Þ ¼ ð2Þ
Nin  Nout
Si ð%Þ  gð%Þ
Yi ð%Þ ¼ ð3Þ
100%
where ni is the fraction of carbon atoms in a product relative to initial hydrocarbon;
N is the molar amount of product formed; (Nin - Nout) is the molar amount of initial
substance (ethane) consumed in the reaction, and g is the ethane conversion. The
selectivity and yield of ethylene were determined after subtracting the amount of
ethylene in the initial gas mixture.

123
1138 V. N. Snytnikov et al.

Figure 3 shows the selectivity and yield of ethylene and methane plotted against
the exposure time of the reaction mixture. Ethylene selectivity decreased from 98 to
70% for contact times of 2–14.6 s, with methane selectivity increasing from 2 to
22%. The selectivity for propylene reached 2% at 4.5 s, further changes being
insignificant. The selectivity for acetylene increased monotonically to 3.7% (Fig. 3).
The yield of ethylene increased sharply from 5 to 60% as exposure time
increased from 2–6 s, followed by only minor changes. The yield of methane tended
continuously to 18%. For acetylene, the yield attained was 2.8% at the exposure
time of reaction mixture up to 4.5%. The yield of propylene gradually increased to
1.5% at 7 s and maintained this value. It seems interesting to compare the
compositions of products obtained in experiments at high values of ethane
conversion with the calculated data for thermodynamical equilibrium conditions.
The calculation was performed using the HYSYS software package [39]. With the
initial ethane–ethylene mixture containing 10% ethylene and reaction products
represented by CH4, C2H6, C2H4, C2H2, C3H6, and H2, the temperature was varied
in the range of 400–1,500 °C.
At 400–900 °C, the main component was methane, up to 60 vol.%. The ethylene
content passed a maximum of 22 vol.% at 700–730 °C. The highest propylene
content was 23 vol.% at 400 °C, followed by a decrease to 0.3 vol.%. Acetylene and
hydrogen rose to 10 vol.%.
The data obtained in the experiments (Fig. 4) substantially differ from the
thermodynamic calculation. The amount of ethane decreased from 90 to 10 vol.%.
The amount of ethylene reached a maximum value of 40 vol.%. The amount of
hydrogen, being in accord with the increasing ethylene concentration, was 25–32
vol.%. The amount of methane was 16 vol.%. The fractions of acetylene and
propylene in the reaction products did not exceed 1.8 and 0.7 vol.%, respectively.
Thus, there is a major discrepancy between the experimental and calculated
compositions of the ethane pyrolysis products in approximation to thermodynam-
ically equilibrium conditions. To solve the problem, kinetic calculation methods
should be devised and applied.

Fig. 3 Selectivity and yield of left CH4 and C2H4 and right C2H2 and C3H6 versus exposure time. Laser
radiation power 73 W. Composition of the initial ethane–ethylene mixture: C2H6—91 vol.%, C2H4—9 vol.%

123
Autocatalytic gas-phase dehydrogenation of ethane 1139

Fig. 4 Left Time dependence of the concentrations of the main products of ethane pyrolysis. The
experimental data are shown by points, curves were obtained by theoretical calculation according to the
developed kinetic scheme. Right Time dependence of the concentrations of by-products

Quantum-chemical simulation results

The important steps in the kinetic scheme for ethane pyrolysis are related to the
interaction of ethane and ethylene. The decomposition of ethane (Eq. 1) is
considered elsewhere as the main chain-initiating step. Unfortunately, it contradicts
the experimental finding of our previous work [31], which indicated that methyl
radicals are produced at activation energy barrier of 250 kJ/mol which is
substantially lower than the activation energy required by Eq. 1, 360 kJ/mol.
Another possible route is the reaction:
C2 H4 þ C2 H6 ! C3 H7  þ CH3  ð4Þ
The activation energy of the reaction of ethane with ethylene was estimated
quantum-chemically as 382 kJ/mol (Table 1).
Nevertheless, the direct reaction of ground state molecules does not exhaust all
possible reaction routes. The energy required to obtain methyl radicals can be
accumulated via a two-step process:
C2 H4 !  C2 H4  ð5Þ

C2 H4  þ C2 H6 ! C3 H7  þ CH3  ð6Þ
with an activation energy of 250 kJ/mol for the rate-limiting step in Eq. 5.

Table 1 Reaction enthalpies 0

Reaction Ea Dr HT¼0
and activation energies obtained
(kJ/mol) (kJ/mol)
via quantum-chemical
simulation
C2 H6 ! 2CH3  356 356
C2 H4 þ C2 H6 ! C3 H7  þ CH3  382 265
C2 H4 !  C2 H4  253 253

C2 H4  þ C2 H6 ! C3 H7  þ CH3  216 4

C2 H4  þ C2 H6 ! 2C2 H5  62 -4

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1140 V. N. Snytnikov et al.

Fig. 5 Ethylene biradical

reactions simulated via
quantum-chemical methods

Collisions of an ethylene molecule with other molecules promote its rotation

along the C=C bond. During the rotation, the electronic state of the molecule is
changed in such a way that atomic p-orbitals no longer overlap with each other. This
is the case for the  C2 H4  triplet state. Note that it is forbidden for this energy to be
lost by emission of light, because it is not allowed for a molecule to change its spin
during electronic transitions. Interaction with other molecules is the only way to
transfer the triplet state energy. Collision-excited ethylene biradical molecules live
long enough to react with ethane. The reactions of triplet ethylene were also
considered with the aid of quantum-chemical methods (Table 1).
The ethylene triplet biradical can attack ethane on either a carbon atom or a
hydrogen atom (Fig. 5). The ethylene biradical substitutes a methyl group or
abstracts hydrogen from ethane which yields two ethyl radicals.

C2 H4  þ C2 H6 ! 2C2 H5  ð7Þ
The activation energy of the reaction producing methyl and propyl radicals is
significantly lower if the biradical form of ethylene participates in the reaction—
only 216 kJ/mol vs. 382 kJ/mol. Pre-exponential factors for Eqs. 5 and 6 are
estimated by use of transition state theory as 6.03 9 1010 9 T and 4.52 9 106 9 T,
respectively. The experimental rate constant for Eq. 5, determined elsewhere [33],
agrees well with our value.
We also considered the formation of butane C4H10. An assumption that the ethane–
ethylene interaction is limited only by the formation of biradical did not allow us to
find the reaction route for butane formation. In the quantum-chemical calculations
aimed at energy optimization, the reaction route did not correspond to the specified
products. A possible reason is that the formation of butane requires substantial
rearrangement of molecules, which occurs under heterogeneous conditions.

A kinetic scheme

Dehydrogenation of ethane is conventionally described by the radical-chain

mechanism, including the step of generation of radical by dissociation of ethane
into two methyl radicals (Eq. 1). This step requires high temperature because of the
high activation energy (Table 2). Here we suggest an alternative scheme for
generation of methyl radicals.

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Autocatalytic gas-phase dehydrogenation of ethane 1141

Table 2 Reactions and corresponding reaction rate constants determined for the autocatalytic radical
mechanism of ethane pyrolysis
Reaction log k (L 9 mol-1 9 s-1 or s-1)

Chain initiation
C2 H6 ! 2CH3  16.0 - 360/(19.14 9 10-3 T)
C2 H4 þ C2 H6 ! C3 H7  þ CH3  7.37 - 382/(19.14 9 10-3 T)
C2 H4 !  C2 H4  11.7 - 253/(19.14 9 10-3 T)

C2 H4  þ C2 H6 ! C3 H7  þ CH3  13.4 - 216/(19.14 9 10-3 T)
Chain propagation
CH3  þ C2 H6 ! C2 H5  þ CH4 10 - 50/(19.14 9 10-3 T)

C2 H5 ! C2 H4 þ H 
13.5 - 170/(19.14 9 10-3 T)

C2 H4 þ H ! C2 H5 
10.4 - 8.4/(19.14 9 10-3 T)

C2 H6 þ H ! H2 þ C2 H5 
11 - 40/(19.14 9 10-3 T)

CH3 þ C2 H4 ! C3 H7 
10.9 - 33/(19.14 9 10-3 T)

C3 H7 ! CH3 þ C2 H4 
13.9 - 137/(19.14 9 10-3 T)

C3 H7 þ C2 H4 ! C2 H5 þ C3 H6 
7.4 - 27.6/(19.14 9 10-3 T)

CH3 þ C2 H4 ! C2 H3 þ CH4 
8.6 - 35/(19.14 9 10-3 T)
Chain termination
C2 H3  þ CH3  ! CH4 þ C2 H2 9.95 - 3.2/(19.14 9 10-3 T)
 
C2 H3 þ H ! C2 H2 þ H2 10
2C2 H5  ! C2 H4 þ C2 H6 10 - 8.4/(19.14 9 10-3 T)

T temperature, K

Scheme I (general). Autocatalytic gas-phase dehydrogenation of ethane.

Initiation
C2 H6 ! 2CH3 
C2 H4 !  C2 H4 

C2 H4  þ C2 H6 ! C3 H7  þ CH3 
Propagation
CH3  þ C2 H6 ! C2 H5  þ CH4
C2 H5 
C2 H4 þ H
C2 H6 þ H ! H2 þ C2 H5 
CH3  þ C2 H4
C3 H7 
C3 H7  þ C2 H4 ! C2 H5  þ C3 H6
CH3  þ C2 H4 ! C2 H3  þ CH4
Termination
C2 H3  þ CH3  ! CH4 þ C2 H2
C2 H3  þ H ! C2 H2 þ H2
2C2 H5  ! C2 H4 þ C2 H6

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1142 V. N. Snytnikov et al.

A satisfactory result for the distribution of the main products (C2H6, C2H4, CH4
and H2) is obtained from a simplified kinetic scheme, where C2H2 and C3H6 are
neglected:
Scheme II (simplified). Autocatalytic gas-phase dehydrogenation of ethane.
Initiation
C2 H6 ! 2CH3 
C2 H4 !  C2 H4 

C2 H4  þ C2 H6 ! C3 H7  þ CH3 
Propagation
CH3  þ C2 H6 ! C2 H5  þ CH4
C2 H5 
C2 H4 þ H
C2 H6 þ H ! H2 þ C2 H5 
C3 H7  ! CH3  þ C2 H4
Termination
2C2 H5  ! C2 H4 þ C2 H6
According to the general scheme, the key reaction is the formation of methyl and
propyl radicals by interaction of ethane and ethylene. Therefore, radical chain is
initiated in two-steps. The first step is ethylene biradical formation (Eq. 5); the
second step is biradical reaction with ethane (Eq. 6). This path is energetically more
advantageous than the generation of radicals by conventional reaction (Eq. 1). The
activation energy for these reactions is approximately 100 kJ/mol lower than for
Eq. 1. This possibility was investigated with the aid of quantum-chemical
simulation. The steps in Eqs. 5 and 6 correspond to the reaction:
C2 H6 þ C2 H4 ! C3 H7  þ CH3  ð8Þ
with the effective rate constant log keff = 13.4 - 247.4/(19.14 9 10-3 T) [31]. At
ethylene concentrations higher than 6–7 vol.% the contribution of these reactions to
generation of methyl radicals becomes greater than that of ethane dissociation.
Therefore, the ethane dehydrogenation route in the presence of ethylene is
autocatalytic:
C2 H6 þ C2 H4 ! 2C2 H4 þ H2 ð9Þ
The reactions of C2H2 and C3H6 formation are widely presented in the literature
together with the rate constants [13, 16, 33, 40]. Our calculations showed that the
steps of acetylene and propylene synthesis by reactions:
C3 H7  þ C2 H4 ! C2 H5  þ C3 H6 ð10Þ
CH3  þ C2 H4 ! C2 H3  þ CH4 ð11Þ
 
C2 H3 þ CH3 ! CH4 þ C2 H2 ð12Þ
 
C2 H3 þ H ! H2 þ C2 H2 ð13Þ
describe the experimental results most accurately (Fig. 4). Propylene is formed by
interaction of propyl radical with ethylene (Eq. 10). Synthesis of acetylene proceeds

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Autocatalytic gas-phase dehydrogenation of ethane 1143

in two steps. First, a vinyl radical is formed in Eq. 11. This is followed by reaction
with a methyl radical (Eq. 12) or with a hydrogen atom (Eq. 13). All these steps are
bimolecular radical reactions with minor activation energies (Table 2). The frac-
tions of acetylene and propylene calculated via Scheme I agree well with the
experimental data.

Discussion

Energy barriers for bimolecular radical reactions:


C2 H4  þ C2 H6 ! C3 H7  þ CH3  ð14Þ
  
C2 H4 þ C2 H6 ! 2C2 H5 ð15Þ
are lower than the energy necessary for formation of the ethylene biradical
(Table 1). Thus, it would be reasonable to relate the activation energy of 250 kJ/mol
observed in our experiments [31] for complex reactions with the formation of the
ethylene triplet biradical.
The energy barrier for Eq. 15 is much lower than that for Eq. 14, leading to
methyl and propyl radicals. So, it seems that this reaction should be introduced into
the kinetic scheme. However, according to calculations, the concentration of ethyl
radicals is controlled by the reverse reaction:
2C2 H5  ! C2 H4 þ C2 H6 ð16Þ
leading to their termination. Thus, the kinetic curves for ethane dehydrogenation are
affected only slightly by the generation of ethyl radicals via Eq. 15 against the route
involving methyl radical. Therefore, Eq. 15 can be safely ignored to simplify the
kinetic scheme. However, generation of methyl radicals via Eq. 14 has a strong
effect on the kinetic curves.
Ethane pyrolysis performed in tube furnaces or over catalysts [41–43] is
accompanied by the formation of small amounts of butane. Thus, the mechanism
describing the process for such heterogeneous conditions usually includes an
elementary step of chain breaking, which leads to C4H10. A distinctive feature of
homogeneous gas-phase dehydrogenation of ethane is the absence of butane in the
reaction products.
Table 3 lists the alternative steps of acetylene and propylene formation. These
steps were taken into account when calculating the distribution of reaction products
as a function of time for the temperature 990 K. The calculation was performed by
use of the ChemPak software package [44], which provides a solution for a set of
differential equations for chemical kinetics.

Propylene

C3H6 synthesis via Eq. 10 was replaced by propyl radical dissociation into C3H6 and
hydrogen.
C3 H7  ! C3 H6 þ H ð17Þ

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1144 V. N. Snytnikov et al.

Table 3 Reactions of
Reaction
propylene, acetylene, and vinyl
radical synthesis
C3 H7  ! C3 H6 þ H
 
CH3 þ C3 H7 ! C3 H6 þ CH4
CH3  þ C2 H3  ! C3 H6
C2 H3  ! C2 H2 þ H
 
C2 H3 þ C2 H5 ! C2 H6 þ C2 H2
2C2 H3  ! C2 H2 þ C2 H4
C2 H4 ! C2 H3  þ H
2C2 H4 ! C2 H3  þ C2 H5 
C2 H4 þ C2 H5  ! C2 H6 þ C2 H3 
T temperature, K
log k (L 9 mol-1 9 s-1
or s-1)
13.2 - 159/(19.14 9 10-3 T)
8.4
10
13.5 - 170/(19.14 9 10-3 T)
20.3
9
13 - 452/(19.14 9 10-3 T)
11.7 - 299/(19.14 9 10-3 T)
11 - 81.2/(19.14 9 10-3 T)

According to the calculation, at 20 s the amount of C3H6 obtained is 5 vol.%, with

C2H2 not exceeding 1.5 vol.%. The amount of ethylene was no higher than 38 vol.%,
whereas in experiments its fraction ranged from 40 to 43 vol.%. The fraction of ethane
was 13 vol.% instead of 18 vol.%, and methane fraction was below 10 vol.%.
When propylene synthesis (Eq. 10) was replaced by disproportionation
CH3  þ C3 H7  ! C3 H6 þ CH4 ð18Þ
this led to complete absence of C3H6. After replacement by:
CH3  þ C2 H3  ! C3 H6 ð19Þ
the resulting amount of acetylene became smaller than the amount of propylene
because of consumption of the C2 H3  radical. Thus, Eqs. 18 and 19 are excluded
from general Scheme I for description of the experimental results.

Acetylene

The formation of acetylene with participation of the vinyl radical is presented in

several reactions.
1. Replacement of Eqs. 12 and 13 by the step of vinyl radical dissociation:
C2 H3  ! C2 H2 þ H ð20Þ
gave a minor excess of synthesized acetylene and propylene over the experi-
mental data, with the amount of ethane remaining higher by 3–5 vol.%. Overall,
such a route of acetylene formation diverges only slightly from the experimental
data.
2. Examination of the next route based on the reaction:
C2 H3  þ C2 H5  ! C2 H6 þ C2 H2 ð21Þ
showed that ethane consumption decreased by 5–8 vol.% and the amount of
ethylene in the reaction products diminished by 3–6 vol.%. These amounts of
acetylene and propylene are close to the experimental values.

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Autocatalytic gas-phase dehydrogenation of ethane 1145

3. The kinetic dependence of ethane pyrolysis calculated after replacement of the

acetylene synthesis step:
2C2 H3  ! C2 H2 þ C2 H4 ð22Þ
showed a twofold decrease in acetylene formation. For a contact time 15 s, the
amount of acetylene was below 1.2 vol.%; the amounts of the other reaction
mixture components were close to the experimental values.
Our calculation demonstrated that distribution of ethane pyrolysis products is
similar for calculation by Scheme I and for successive exclusion of acetylene
synthesis steps. Thus, both reactions are included in Scheme I.

Vinyl radical

According to the NIST database, there are several routes of C2 H3  formation.

Replacement of vinyl radical generation, Eq. 11, by the equation for ethylene
dissociation:
C2 H4 ! C2 H3  þ H ð23Þ
or by disproportionation of two ethylene molecules:
2C2 H4 ! C2 H3  þ C2 H5  ð24Þ
led to the absence of acetylene from the reaction products. Whereas the synthesis of
C2 H3  with C2H6 via:
C2 H4 þ C2 H5  ! C2 H6 þ C2 H3  ð25Þ
stopped the process: ethane conversion was limited to a few percent only. The rate
constants of the reactions considered here are listed in Table 3.
Therefore, Scheme I of autocatalytic gas-phase dehydrogenation of ethane
provides a complete description of the experimental data [31] for gas-phase pyrolysis
of ethane in a mixture with ethylene at atmospheric pressure and temperatures up to
1,000 K. Distribution of the reaction products is shown in Fig. 4. Experimental data
on changes in the composition of reaction medium with time for the initial ethane–
ethylene mixture with the starting 9 vol.% content of ethylene and calculation by
Scheme I are in good agreement, including the characteristic time for the ethane
fraction decrease and build-up of reaction products.

Conclusion

Gas-phase pyrolysis of ethane by continuous CO2 laser irradiation was used for bulk
heating of the reaction mixture. The use of CO2 laser irradiation energy provides
homogeneous conditions for the study of gas-phase reactions and excludes the
effects of heterogeneous processes. High efficiency of CO2 laser radiation energy
transfer to the reaction medium by ethylene, a pyrolysis product, was demonstrated.

123
1146 V. N. Snytnikov et al.

Ethane dehydrogenation at atmospheric pressure with 70–82% conversion was

characterized by an ethylene yield of 57%.
The distribution of reaction products obtained with an assumed thermodynamic
equilibrium at temperatures up to 1,000 °C was far from the distribution observed
experimentally. Therefore, the estimates of ethane conversion and yield, and
selectivity of main reaction products were based on the kinetic scheme with additional
experimental substantiation.
A simple kinetic scheme for the mechanism of ethane thermal pyrolysis in the
gas phase at atmospheric pressure with high conversion was suggested. Gas-phase
dehydrogenation of ethane is an autocatalytic process with regard to ethylene. The
ethylene biradical is extremely important in this scheme. Reaction of this biradical
with ethane produces methyl and propyl radicals, which are essential for further
transformations during the ethane dehydrogenation process. By using quantum
chemical simulation it was shown that a biradical two-step mechanism of formation
of methyl radicals was more appropriate than straightforward ethane dissociation by
100 kJ/mol.
The simple scheme developed is able to predict qualitatively the distribution of
the main products (ethylene, hydrogen, and methane) as well as secondary by-
products, for example acetylene and propylene, which are formed in small amounts.

Acknowledgment The authors acknowledge the Russian Federation President Grant for the Leading
Scientific Schools for funding (NSh 3156.2010.3).

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