Kinetics of the High-Temperature Heterogeneous Reaction of Chlorine and Nickel between 1200 and 1700°K

McKinley, J. D.; Shuler, Kurt E.

doi:10.1063/1.1744369

Cited by 25 publications

(31 citation statements)

References 5 publications

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“…These results, which ar-consistent with those of Ref. 6, reveal significant differences between the nickel and molybdenum chlorination reactions.…”

Section: Tp-117supporting

confidence: 82%

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Kinetics of the Attack of Molybdenum by Dissociated Chlorine¹

Rosner¹,

Allendorf²

1965

J. Phys. Chem.

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The true kinetics of the attack of molybdenum surfaces by both atomic and diatomic chlorine have been studied using microwave discharge-fast flow system techniques coupled with electrical resistance heating and monitoring of the reacting specimens. Experimental results are reported herein over the surface temperature range from 400 0 K to 1530 0 K, at reactant partial pressures of the order of 10-to 10-1 Torr. In contrast to the behavior of nickel, dissociation markedly increases the chlorination probability of molybdenum over the entire temperature range investigated, the enhancernent being of the order of 100-fold at about 1000 0 K. The high reaction probability for Clz(g) attack of high temperature nickel, previously reported by McKinley and Shuler, has been verified. When exposed to dissociated chlorine the ratio of the nickel chlorination rate to the Cl-atom recombination rate decreases with decreasing surface temperature-on 420 0 K nickel filaments the recombination coefficient y has been found to be 1/ 2 . The implications of these results with regard to dissociative adsorption and evaporation on/from nickel and molybdenum surfaces are discussed in the light of available kinetic and thermochemical data for these and related heterogeneous reactions.

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“…These results, which ar-consistent with those of Ref. 6, reveal significant differences between the nickel and molybdenum chlorination reactions.…”

Section: Tp-117supporting

confidence: 82%

“…In addition, we have determined the recombination coefficient for Cl-atoms on nickel, and confirmed the high reaction probability for ClZ on nickel filaments above 1000°0 X, first reported by McKinley and Shuler. 6 …”

Section: Tp-117mentioning

confidence: 99%

Kinetics of the Attack of Molybdenum by Dissociated Chlorine¹

Rosner¹,

Allendorf²

1965

J. Phys. Chem.

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“…The authors also note that this mechanism is dependent on a number of experimental parameters and can change – e.g., for high gas flow rates. Additionally, gas composition (and therefore partial pressures), total pressure, gas temperature, and flow rate have been found to have a strong impact on the corrosion rate . In Figs.…”

Section: Introductionmentioning

confidence: 95%

Kinetics of volatilization of high temperature corrosion products and its application to chlorine corrosion

Rammer

Galetz

2016

Materials & Corrosion

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Operating atmospheres of many industrial high temperature processes contain a certain amount of halogens, in most cases chlorine. Halogens have the tendency of forming volatile metal chlorides of the general formula MxCly, which are well known to play a critical role in high temperature corrosion processes, when present at a significant amount. Thermodynamic calculations give a valuable hint, whether a reaction product can occur and how volatile such products can potentially be, when the partial pressures are calculated. However, such calculations reflect thermodynamically stable conditions, while in open systems the local kinetics control the process of surface reactions. For each specific condition, the reaction rates and thus the corrosion rates have to be determined. In previous work, we have shown that corrosion kinetics which lead to the formation of volatile products follows different steps. In this work, a mathematical model is developed in which the different steps, which are required for the formation of metal chlorides and their removal from the surface are described. It is assumed that the slowest of such formation or transport steps determines the kinetics of high temperature corrosion. The application of this model on the literature data shows that by this model it becomes possible to identify the slowest and therefore rate determining step.

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“…In addition, on obvious effect of temperature on the rate constant of weight loss was observed. Small activation energies for the chlorination reaction of Cu by Cl 2 have been reported by Frommer and Polanyi [20], and for that of Ni by Cl 2 by McKinley and Shuler [21]; in both reactions the activation energy was no more than 8 kJ=mol. As discussed by Fruehan and Martonik [17][18][19], it is considered that the rate determining step is the diffusion of gaseous species inside the boundary layer in the gas phase because of the large molecular weight of chloride vapor.…”

Section: Chlorination and Evaporation Behaviors Of Zinc Oxide In Ar-hmentioning

confidence: 67%

Chlorination and Evaporation Behaviors of Zinc Oxide in Ar- HCl-O2 Atmosphere

Yajima¹,

Matsuura²,

Tsukihashi³

2011

High Temperature Materials and Processes

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The chlorination and evaporation behaviors of zinc oxide in an Ar-HCl-O 2 atmosphere were observed by gravimetry. The rate of weight loss increased with increasing partial pressure of hydrogen chloride in an Ar-HCl atmosphere. When the partial pressure of hydrogen chloride in an Ar-HCl atmosphere was the same as that of chlorine in an Ar-Cl 2 atmosphere, the rate of weight loss in the Ar-HCl atmosphere was larger than that in the Ar-Cl 2 atmosphere although the chlorine content in the Ar-HCl atmosphere was half that in the Ar-Cl 2 atmosphere. From the dependence of the rate of weight loss on the partial pressure of hydrogen chloride, it was considered that the rate determining step of the reaction is the diffusion of gaseous species inside the boundary layer in the gas phase. By increasing the partial pressure of oxygen in an Ar-HCl-O 2 atmosphere, the rate of weight loss slightly increased. This tendency was similar to that in an Ar-Cl 2 -O 2 atmosphere. On the other hand, the chlorination rate of zinc oxide, estimated by assuming equilibrium of the gas phase, and the measured chlorination rates of Ar-HCl and Ar-Cl 2 gases decreased because of the decrease in partial pressure of hydrogen chloride by the oxidation of HCl gas. It is considered that the increase in the chlorination rate is due to the formation of the oxychloride ZnOCl together with ZnCl 2 in the oxidizing atmosphere.

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Kinetics of the High-Temperature Heterogeneous Reaction of Chlorine and Nickel between 1200 and 1700°K

Cited by 25 publications

References 5 publications

Kinetics of the Attack of Molybdenum by Dissociated Chlorine¹

Kinetics of the Attack of Molybdenum by Dissociated Chlorine¹

Kinetics of volatilization of high temperature corrosion products and its application to chlorine corrosion

Chlorination and Evaporation Behaviors of Zinc Oxide in Ar- HCl-O2 Atmosphere

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Kinetics of the High-Temperature Heterogeneous Reaction of Chlorine and Nickel between 1200 and 1700°K

Cited by 25 publications

References 5 publications

Kinetics of the Attack of Molybdenum by Dissociated Chlorine1

Kinetics of the Attack of Molybdenum by Dissociated Chlorine1

Kinetics of volatilization of high temperature corrosion products and its application to chlorine corrosion

Chlorination and Evaporation Behaviors of Zinc Oxide in Ar- HCl-O2 Atmosphere

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Product

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Kinetics of the Attack of Molybdenum by Dissociated Chlorine¹

Kinetics of the Attack of Molybdenum by Dissociated Chlorine¹