Reaction Kinetics of Atomic chlorine on Si(100)2×1

1992 ◽  
Vol 280 ◽  
Author(s):  
Kazuhiro Karahashi ◽  
Jiro Matsuo ◽  
Kei Horiuchi

ABSTRACTThe interaction of atomic chlorine with Si(100)2×1 surfaces was studied by using chlorine atom beams. The etching reaction of silicon substrates has been observed when chlorine atoms impinged on the chlorinated surface, at substrate temperatures below 600°C. The major desorption product is SiCl2. Studies of the temperature dependence of the reaction showed that the activation energy are 0.08 eV at 0.4 ML and 0.2 eV at 0.8 ML. These extremely low activation energies suggest that the surface reaction is mainly driven by the internal energy of incident atomic chlorine instead of thermal excitation from Si(100) solid surface. Therefore chlorine atoms enter the transition state without equilibrating at the surface prior to the reaction. The reaction strongly depends on the chlorine coverage on the surface. The reaction occurred above 0.3 ML. The etching probability of the surface reached a maximum at 0.4 ML, and decreased with increasing coverage.

1997 ◽  
Vol 470 ◽  
Author(s):  
R. Schwarz ◽  
A. Dittrich ◽  
S. M. Zhou ◽  
M. Hundhausen ◽  
L. Ley ◽  
...  

ABSTRACTSuicide formation during thermal annealing of thin Pt layers deposited by evaporation onto crystalline silicon substrates was studied by in-situ spectral ellipsometry. As was shown in an earlier study, Pt suicide is formed in a two-step process with intermediate stages of Pt2Si and PtSi at temperatures of about 190 and 240 °C, respectively. We observed a shift of about 15 °C of the di- and monosilicide formation, when the anneal rate was lowered from 3 to 1 K/min. The analysis of the reaction kinetics using the normalized ellipsometric angle δ yields a good fit to the data for different anneal rates with an activation energy of (1.6 ± 0.2) eV. The underlying model of suicide formation through a multilayer system was checked with depth profiles and compositional information obtained from Rutherford Backscattering.


1957 ◽  
Vol 35 (11) ◽  
pp. 1341-1350 ◽  
Author(s):  
M. J. Dignam ◽  
W. G. Forbes ◽  
D. J. Le Roy

The general features of the mechanism of the over-all process [Formula: see text][Formula: see text] are similar to those for the over-all process [Formula: see text][Formula: see text] studied previously. The reaction is inhibited by HCl. Chains are terminated by two processes, one of which is first order, the other second order in atomic chlorine. The first order process is not entirely diffusion controlled and a theory is advanced to account for its nature; the homogeneous combination of chlorine atoms requires a third body, mono- and di-chloromethyl chloroformate being particularly effective. The activation energy for hydrogen abstraction from monochloromethyl chloroformate by atomic chlorine is 5.2 kcal. per mole. The C—H bond dissociation energy in monochloromethyl chloroformate is estimated to be 99.8 ± 4.5 kcal. per mole.


2015 ◽  
Vol 17 (2) ◽  
pp. 911-917 ◽  
Author(s):  
J. M. Nicovich ◽  
S. Mazumder ◽  
P. L. Laine ◽  
P. H. Wine ◽  
Y. Tang ◽  
...  

The first kinetic data for the gas phase reactions of amines with chlorine atoms.


1982 ◽  
Vol 47 (7) ◽  
pp. 1780-1786 ◽  
Author(s):  
Rostislav Kudláček ◽  
Jan Lokoč

The effect of gamma pre-irradiation of the mixed nickel-magnesium oxide catalyst on the kinetics of hydrogenation of maleic acid in the liquid phase has been studied. The changes of the hydrogenation rate are compared with the changes of the adsorbed amount of the acid and with the changes of the solution composition, activation energy, and absorbed dose of the ionizing radiation. From this comparison and from the interpretation of the experimental data it can be deduced that two types of centers can be distinguished on the surface of the catalyst under study, namely the sorption centres for the acid and hydrogen and the reaction centres.


Author(s):  
Niels Engholm Henriksen ◽  
Flemming Yssing Hansen

This chapter reviews the microscopic interpretation of the pre-exponential factor and the activation energy in rate constant expressions of the Arrhenius form. The pre-exponential factor of apparent unimolecular reactions is, roughly, expected to be of the order of a vibrational frequency, whereas the pre-exponential factor of bimolecular reactions, roughly, is related to the number of collisions per unit time and per unit volume. The activation energy of an elementary reaction can be interpreted as the average energy of the molecules that react minus the average energy of the reactants. Specializing to conventional transition-state theory, the activation energy is related to the classical barrier height of the potential energy surface plus the difference in zero-point energies and average internal energies between the activated complex and the reactants. When quantum tunnelling is included in transition-state theory, the activation energy is reduced, compared to the interpretation given in conventional transition-state theory.


2021 ◽  
pp. 009524432110203
Author(s):  
Sudhir Bafna

It is often necessary to assess the effect of aging at room temperature over years/decades for hardware containing elastomeric components such as oring seals or shock isolators. In order to determine this effect, accelerated oven aging at elevated temperatures is pursued. When doing so, it is vital that the degradation mechanism still be representative of that prevalent at room temperature. This places an upper limit on the elevated oven temperature, which in turn, increases the dwell time in the oven. As a result, the oven dwell time can run into months, if not years, something that is not realistically feasible due to resource/schedule constraints in industry. Measuring activation energy (Ea) of elastomer aging by test methods such as tensile strength or elongation, compression set, modulus, oxygen consumption, etc. is expensive and time consuming. Use of kinetics of weight loss by ThermoGravimetric Analysis (TGA) using the Ozawa/Flynn/Wall method per ASTM E1641 is an attractive option (especially due to the availability of commercial instrumentation with software to make the required measurements and calculations) and is widely used. There is no fundamental scientific reason why the kinetics of weight loss at elevated temperatures should correlate to the kinetics of loss of mechanical properties over years/decades at room temperature. Ea obtained by high temperature weight loss is almost always significantly higher than that obtained by measurements of mechanical properties or oxygen consumption over extended periods at much lower temperatures. In this paper, data on five different elastomer types (butyl, nitrile, EPDM, polychloroprene and fluorocarbon) are presented to prove that point. Thus, use of Ea determined by weight loss by TGA tends to give unrealistically high values, which in turn, will lead to incorrectly high predictions of storage life at room temperature.


Metals ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 1176
Author(s):  
Fuqiang Zheng ◽  
Yufeng Guo ◽  
Feng Chen ◽  
Shuai Wang ◽  
Jinlai Zhang ◽  
...  

The effects of F− concentration, leaching temperature, and time on the Ti leaching from Ti-bearing electric furnace slag (TEFS) by [NH4+]-[F−] solution leaching process was investigated to reveal the leaching mechanism and kinetics of titanium. The results indicated that the Ti leaching rate obviously increased with the increase of leaching temperature and F− concentration. The kinetic equation of Ti leaching was obtained, and the activation energy was 52.30 kJ/mol. The fitting results of kinetic equations and calculated values of activation energy both indicated that the leaching rate of TEFS was controlled by surface chemical reaction. The semi-empirical kinetics equation was consistent with the real experimental results, with a correlation coefficient (R2) of 0.996. The Ti leaching rate reached 92.83% after leaching at 90 °C for 20 min with F− concentration of 14 mol/L and [NH4+]/[F−] ratio of 0.4. The leaching rates of Si, Fe, V, Mn, and Cr were 94.03%, 7.24%, 5.36%, 4.54%, and 1.73%, respectively. The Ca, Mg, and Al elements were converted to (NH4)3AlF6 and CaMg2Al2F12 in the residue, which can transform into stable oxides and fluorides after pyro-hydrolyzing and calcinating.


Ceramics ◽  
2021 ◽  
Vol 4 (2) ◽  
pp. 331-363
Author(s):  
Eugeniy Lantcev ◽  
Aleksey Nokhrin ◽  
Nataliya Malekhonova ◽  
Maksim Boldin ◽  
Vladimir Chuvil'deev ◽  
...  

This study investigates the impact of carbon on the kinetics of the spark plasma sintering (SPS) of nano- and submicron powders WC-10wt.%Co. Carbon, in the form of graphite, was introduced into powders by mixing. The activation energy of solid-phase sintering was determined for the conditions of isothermal and continuous heating. It has been demonstrated that increasing the carbon content leads to a decrease in the fraction of η-phase particles and a shift of the shrinkage curve towards lower heating temperatures. It has been established that increasing the graphite content in nano- and submicron powders has no significant effect on the SPS activation energy for “mid-range” heating temperatures, QS(I). The value of QS(I) is close to the activation energy of grain-boundary diffusion in cobalt. It has been demonstrated that increasing the content of graphite leads to a significant decrease in the SPS activation energy, QS(II), for “higher-range” heating temperatures due to lower concentration of tungsten atoms in cobalt-based γ-phase. It has been established that the sintering kinetics of fine-grained WC-Co hard alloys is limited by the intensity of diffusion creep of cobalt (Coble creep).


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