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Chlorination of Zinc Oxide between 723 and 973 K

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Abstract

The kinetics of the chlorination of zinc oxide has been studied by thermogravimetry between 723 and 973 K. The starting temperature for the reaction of ZnO with chlorine is determined at about 498 K. The influence of gaseous flow rate, sample mass, temperature, and chlorine partial pressure in the reaction rate is analyzed. It is established that the reaction occurs under mixed control, being pore diffusion coupled with chemical reaction as the rate controlling step. An apparent reaction order of 0.5 with respect to chlorine partial pressure was determined. A kinetic model for the chlorination reaction of porous solids under mixed control determined an intrinsic reaction order of zero with respect to partial pressure of chlorine and an intrinsic activation energy of 249 kJ mol−1.

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Abbreviations

C :

concentration of Cl2, mol cm−3

C 0 :

concentration of Cl2 in the bulk, mol cm−3

\( D_{{\text{Cl}}_2} \) :

ordinary diffusion coefficient of Cl2 in the reaction mixture, cm2 s−1

D e :

effective diffusivity of Cl2 into the sample pores, cm2 s−1

D K :

Knudsen diffusion coefficient of Cl2 through sample pores, cm2 s−1

E :

activation energy, kJ mol−1

E ap :

apparent activation energy, kJ mol−1

k(T):

reaction rate constant, mol s−1 cm−2

K*:

apparent rate constant, s−1

M x :

molecular weight of specie x, g mol−1

m 0 :

initial mass of the sample, g

n :

intrinsic reaction order, dimensionless

n ap :

apparent reaction order, dimensionless

pCl2 :

partial pressure of chlorine, kPa

P 0 :

partial pressure of chlorine in bulk, kPa.

r 0 :

sample radius, cm

r p :

pore radius, cm

R :

reaction rate, s−1

R m :

molar reaction rate, mol Cl2 reacted s−1

Rg :

gas constant, 82 cm3 atm K−1 mol−1

S e :

external surface, cm2

S v :

surface area per unit volume in the reaction zone, cm−1

t :

time, min or s

t 0.5 :

mean reaction time, s

T :

temperature, K

X :

distance normal to the external surface, cm

α :

reaction degree, dimensionless

ΔG°:

standard free energy change, kJ mol−1

ρ M :

molar density of ZnO sample

ρ ap :

apparent density, g cm−3

τ :

tortuosity factor, dimensionless

ω :

porosity, dimensionless

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Acknowledgments

The authors thank the Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), and Universidad Nacional del Comahue for the financial support of this work. They also thank Daniel Serrano from “Lab. Materiales Porosos,” Centro Atómico Bariloche, for the pore size distribution analyses of the powder samples.

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Authors and Affiliations

  1. Comisión Nacional de Energía Atómica (C.N.E.A.), Avenida Bustillo 9500, (8400), San Carlos de Bariloche, Argentina

    G. de Micco (Researcher), G.G. Fouga (Researcher) & A.E. Bohé (Researcher)

  2. Universidad Nacional de Cuyo, Instituto Balseiro, Avenida Bustillo 9500, (8400), San Carlos de Bariloche, Argentina

    G. de Micco (Researcher)

  3. Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Buenos Aires, Argentina

    G.G. Fouga (Researcher) & A.E. Bohé (Researcher)

  4. Universidad Nacional del Comahue, Centro Regional Universitario Bariloche, (8400), San Carlos de Bariloche, Argentina

    G.G. Fouga (Researcher) & A.E. Bohé (Researcher)

Authors
  1. G. de Micco
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  2. G.G. Fouga
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  3. A.E. Bohé
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Corresponding author

Correspondence to G. de Micco.

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Manuscript submitted August 6, 2006.

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de Micco, G., Fouga, G. & Bohé, A. Chlorination of Zinc Oxide between 723 and 973 K. Metall Mater Trans B 38, 853–862 (2007). https://doi.org/10.1007/s11663-007-9089-3

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