7.

3l4
Inorganic Gas-Phase Plasma Decomposition Processes
COMPLETE CO1 DISSOCIATION IN PLASMA WITH PRODUCTION
OF CARBON AND OXYGEN
5.7. I. Complete Plasma-Chemical Dissociation of CO1: Specifics
of the Process and Elementary Reaction Mechanism
Plasma parameters can be chosen to provide a predominantly complete dissociation of CO2
with the production of solid carbon and oxygen:
coz s c(S) + oz, AH i 11.5 eV/mol. (5-100)
This plasma-chem ical process not only attracts attention itself for application in chemi-
cal technology but it also can be applied as an engineering model for the production of metals
from their oxides and halogenides (Tsvetkov & Panfilov, l98O). The plasma-chemical mech-
anism for the complete dissociation process (5-lOO) includes all reactions leading to the
form ation of CO (see, in particular, Table 5-l). First of all, it includes elementary reactions
(5-6) and (5-7), which can be effectively stimulated by vibrational excitation Linder non-
equilibrium plasma conditions. For complete dissociation of carbon dioxide, the conversion
of CO into elementary carbon should also take place. This process is usually kinetically lim-
ited (Legasov et al., l977a,b) because of the record high value (ll eV!) of bonding energy
in a CO molecule. Conversion of CO into carbon can be effectively performed by means
of the reaction of disproportioning, which can be, in particular, significantly accelerated by
the vibrational excitation of CO molecules:
CO -- CO e CO2 -- C, AH : 5.5 eV/mol, Ea : 6eV/mol. (5-lOl)
The activation energy of disproportioning reaction (5-lOl) is still high, but it is almost
two-fold less than the CO bonding energy mentioned earlier (Walker, Rusinko, & Austin,
l963). Elementary reaction (5-lOl) leads to the formation of free carbon atoms in the
gas phase. The kinetics of stimulation of the elementary process of disproportioning
(5-lOl) by vibrational excitation of CO molecules will be discussed in the next section.
The disproportioning (5-lOl) can also be accelerated via electronic excitation:
CO(a3l'l) + co s coz + c. (5-102)
This elementary process dominates, however, at relatively high values of electron tem-
perature in plasma (Volchenok & Egorov, l976). In general, the disproportioning of CO
with the production of elementary carbon (5-lOl) can be easily stimulated in different
plasma systems (Maximov et al., l979, Legasov et al., l98l). It is much more difficult to
provide reduction of elementary carbon not from CO, but directly from CO2. The major
complication in this case is due to the fast reverse reaction of carbon atoms:
C -- CO2 e CO -- CO, Ea : 0.5 eV/mol. (5-lO3)
Effective suppression of the reverse reaction (5-103) becomes possible only by hetero-
geneous stabilization of atomic carbon produced in (5-101) on discharge Walls or by carbon
clusterization in the discharge volume. The kinetics of heterogeneous carbon stabilization
and clusterization is considered in detail in Legasov et al. (l978c).
5.7.2. Kinetics of CO Disproportioning Stimulated in Non-Equilibrium
Plasma by Vibrational Excitation of Molecules
The efficiency of vibrational energy in overcoming the activation energy barriers of strongly
endothermic reactions is usually close to lOO% (oz : l; see Chapter 2). Usually only one
molecule retains the vibrational energy, as in the case of CO2 dissociation (see Section 5. l .4,