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Introduction Ulrich [3⫺7] et al. Since the kinetics of the molecular com-
bustion reaction influences the flame and the temperature
The formation of silica in a high-temperature combustion field in the reactor, it is necessary to investigate this step in
process to produce extremely fine particle sized fumed silica more detail. It is of particular interest, on which time scale
or pyrogenic silica is well established as the AEROSIL the formation of molecular SiO2 takes place. To make a
process. In the past 60 years AEROSIL has gained a broad first step towards this goal, a simple kinetic model was de-
variety of applications, and the global production capacity veloped.
of fumed silicas exceeded 100,000 mt. Although the pro- To our knowledge, there is no kinetic data regarding the
cessing of AEROSIL using chlorosilanes as volatile raw combustion of SiCl4 in a H2/O2 flame available in the litera-
materials has been well investigated, very little is known ture. However, Binnewies et al. [8] state that the reaction of
about the basic reactions of this process. SiCl4 with water might be an important reaction in this pro-
To understand the formation of AEROSIL, it is import-
cess. On the other hand, Powers found that during the com-
ant to know about the underlying molecular mechanisms.
bustion process of SiCl4 in oxygen, the dissociation of SiCl4
Before AEROSIL is formed, a complex combustion pro-
into SiCl3 and Cl is the rate determining step [9].
cess takes place. Actual models of AEROSIL burners as-
It can be expected that many intermediate species will
sume a spontaneous formation of SiO2 molecules that will
occur during the combustion process. For instance, Junker
coagulate in order to form particles [1]. The role of molecu-
et al. detected silaphosgene (O⫽SiCl2) when SiCl4 is
lar SiO2 and protoparticles is discussed by Sheka [2] resp.
brought to reaction with oxygen at high temperatures [10].
In our work, we examined three possible reaction chan-
nels for the combustion of SiCl4 in the H2/O2 flame. Kinetic
* Dr. Bernd Hannebauer parameters have been computed for several elementary re-
Industriepark Wolfgang GmbH, Degussa Group actions using quantum mechanical methods. In the next
Rodenbacher Chaussee 4
D-63457 Hanau, Germany
step, kinetic models were applied to calculate concentration
E-mail: bernd.hannebauer@degussa.com and temperature as a function of time. To reduce the com-
Fax: ⫹49-6181-5972041 plexity, an adiabatic system and a plug flow situation in the
Z. Anorg. Allg. Chem. 2003, 629, 1485⫺1490 DOI: 10.1002/zaac.200300053 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1485
B. Hannebauer, F. Menzel
2. Dissociation
SiCl4 씮 SiCl3 ⫹ Cl
1486 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim zaac.wiley-vch.de Z. Anorg. Allg. Chem. 2003, 629, 1485⫺1490
The Combustion of SiCl4 in Hot O2/H2 Flames
Table 1 Calculated activation energies and Arrhenius factors our calculations. The temperature dependency of heat ca-
pacities can be represented in the standard form
Reaction EA A
kJ/mol s⫺1 cp(T)⫽ A ⫹ 10⫺3·BT ⫹ 10⫺5·CT⫺2 ⫹ 10⫺6·DT2 .
SiCl4 ⫹ H2O 씮 SiCl3OH ⫹ HCl 128 8.2·1011 Table 2 lists the calculated heat capacities expressed by
SiCl3OH 씮 SiCl2O ⫹ HCl 209 2.8·1013 A, B, C and D.
SiCl2O ⫹ H2O 씮 SiClOOH ⫹ HCl 70 2.4·1012
SiClOOH 씮 SiO2 ⫹ HCl 205 3.7·1013
SiCl4⫹OH 씮 SiCl3OH⫹Cl 188 1.4·107
SiCl4 씮 SiCl3 ⫹ Cl ⬵402 ⫺
IV Kinetic modeling
The kinetic modeling was done with the Kintecus software
[16]. The activation energies and Arrhenius parameters of
Table 2 Calculated thermochemical data. A, B, C and D describe the elementary reactions described above as well as the
the temperature dependency of cp according to cp(T)⫽ A ⫹ thermodynamic data for all molecules are needed as input
10⫺3·BT ⫹ 10⫺5·CT⫺2 ⫹ 10⫺6·DT2.
for this simulation. Besides the reactions explicitly men-
∆H0(298) ∆S0(298) A B C D tioned above, the elementary reactions of the H2/O2 reac-
kJ/mol J/mol/K tion are needed. The Chemkin H2O model was used for this
purpose [11].
SiClOOH ⫺608 310 74.518 26.545 0 ⫺5.830
SiCl2O ⫺431 312 72.007 11.196 0 ⫺2.764 Since the reaction
SiCl3OH ⫺785 375 104.681 21.569 0 ⫺4.642
SiCl4 씮 SiCl3 ⫹ Cl
Z. Anorg. Allg. Chem. 2003, 629, 1485⫺1490 zaac.wiley-vch.de 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1487
B. Hannebauer, F. Menzel
Fig. 4 Concentration curves for Model 1, Tstart ⫽ 1000 K. Fig. 7 Temperature curve for Model 1, Tstart ⫽ 2000 K.
Fig. 5 Temperature curve for Model 1, Tstart ⫽ 1000 K. Fig. 8 Concentration curves for Model 2, Tstart ⫽ 1000 K.
1488 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim zaac.wiley-vch.de Z. Anorg. Allg. Chem. 2003, 629, 1485⫺1490
The Combustion of SiCl4 in Hot O2/H2 Flames
References
Fig. 11 Temperature curve for Model 2, Tstart ⫽ 2000 K.
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