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Catalysis Communications 9 (2008) 8284 www.elsevier.com/locate/catcom

LangmuirHinshelwood kinetics A theoretical study

K. Vasanth Kumar
a

a,*

, K. Porkodi b, F. Rocha

a,*

Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, s/n 4200-465 Porto, Portugal b CIQ-UP, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre 687, 4169-007 Porto, Portugal Received 4 December 2006; received in revised form 18 April 2007; accepted 7 May 2007 Available online 17 May 2007

Abstract The present study reports that it is impossible and inappropriate to approximate the LangmuirHinshelwood kinetics to zero order kinetics. 2007 Elsevier B.V. All rights reserved.
Keywords: Heterogeneous catalysis; LangmuirHinshelwood kinetics; Theory; Zero order kinetics

LangmuirHinshelwood (LH) kinetics is the most commonly used kinetic expression to explain the kinetics of the heterogeneous catalytic processes. The LangmuirHinshelwood expression that explains the kinetics of heterogeneous catalytic systems is given by: r dC k r KC ; dt 1 KC 1

1 1 1 : r0 k r k r KC 0

where r represents the rate of reaction that changes with time. The term r in Eq. (1) was represented in terms of initial reaction rate, r0, as a function of the initial dye concentration, C0, or in terms of Ce, where Ce is the equilibrium dye concentration in solution after the completion of dark experiments. The initial rate of reaction as a function of C0 and Ce is given by Eqs. (2) and (3), respectively: r0 k r KC 0 ; 1 KC 0 k r KC e : r0 1 KC e 2 3

The parameters kr and K which are a function of C0 or Ce can be predicted by linearizing the Eq. (2) or (3) as follows:
Corresponding authors. E-mail addresses: vasanth_vit@yahoo.com (K.V. Kumar), frocha@ fe.up.pt (F. Rocha). 1566-7367/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2007.05.019
*

Most of researchers approximated Eq. (1) to rst order kinetics for the condition KC ( 1 [17]. Recently, some papers reported that the LH kinetics as in Eq. (2) can be approximated to zero order kinetics for KC0 ) 1. However, if the LH expression is written in terms of initial reaction rate, for KC0 ) 1, the Langmuir Hinshelwood kinetics will not reduce to a zero order kinetics [812]. As a case study, the literature data for the photocatalytic degradation of Eosin Y by TiO2 P25 catalyst [7] was used. Fig. 1 shows the plot of r0 versus Ce for various K values. The gure shows the simulated r0 values using Eq. (3), for experimental values and also for increasing K values. From Fig. 1, it can be observed that increasing the K values from 2 to 4 times the experimental K value, the simulated r0 deviated much from the experimental kinetics. This shows the signicance of the KCe in the LH expression as in Eq. (3), and suggests that the term KCe in a LangmuirHinshelwood kinetics represented in the form of initial reaction rate should not be neglected. In the case of Eq. (1), the constants kr and K can be calculated from the corresponding integrated expression. This equation can be integrated between the limits: C = C0 at t = 0 and C = C at t = t. The integrated expression is given by:

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Notations Ce C0 C K equilibrium dye concentration in solution after the completion of dark experiments, mg/L initial dye concentration, mg/L concentration at any time t during degradation, mg/L equilibrium constant for adsorption of the substrate onto catalyst  KC 0 C k r Kt: 5 kr limiting rate constant of reaction at maximum coverage under the given experimental conditions. rate of reaction, mg/L min initial rate of reaction, mg/L min contact time, min zero order reaction rate constant, min1

r r0 t k0

 ln

C0 C

If the term KC ( 1 then Eq. (1) is reduced to: r k r KC: 6

used to predict the constants kr and K in the LH expression. In addition, for KC ) 1, the LangmuirHinshelwood kinetics cannot be reduced to zero order kinetics. If the kinetics of studied system follows zero order kinetics, then the rate expression should be expressed as: r dC k0: dt 7

Integrating Eq. (6) with respect to limits: C = C0 at t = 0 and C = C at t = t, LH expression reduces to a rst order kinetics and is given by:   C ln k 1 t; C0 where k1 = krK If the term krK ) 1, then the denominator of Eq. (1) becomes more signicant in predicting the LH kinetics. Thus it is to be remembered that for KC ) 1, Eq. (1) cannot be reduced to zero order kinetics as mentioned in some of referred papers [813]. If KC ) 1, then Eq. (5) is to be
1 0.9 0.8 0.7 ro, mg/L.min 0.6 0.5 0.4 0.3 0.2 0.1 0 0 20 40

Thus the rate r in Eq. (7) is not related to r or r0 as in Eq. (2) or Eq. (3), respectively, based on the kinetic theories behind these expressions. The constants kr and K should not be approximated to a single constant by ignoring the term KC in the denominator of the LangmuirHinshelwood kinetics. Though the experimental kinetic data is linear, the rate of reaction cannot be made equivalent to Eq. (2) or (3), instead the rate of reaction as in Eq. (7) can be used to approximate the experimental kinetics. Based on the

K: Experimental K: 2*Experimental K: 3*Experimental K: 4*Experimental

60 Ce, mg/L

80

100

Fig. 1. Plot of r0 versus Ce for the photocatalytic degradation of 50 mg L1 (7.22 105 M) Eosin Y by TiO2 P25 for dierent K values in the presence of 1 g l1 TiO2 P25 [7].

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K.V. Kumar et al. / Catalysis Communications 9 (2008) 8284 [6] S. Senthilkumaar, K. Porkodi, R. Gomathi, A.G. Maheswari, N. Manonmani, Dyes Pigments 69 (2006) 22. [7] I. Poulios, E. Micropoulou, R. Panou, E. Kostopoulou, Appl. Catal. B 41 (4) (2003) 345. [8] V. Iliev, D. Tomova, L. Bilyarska, A. Eliyas, L. Petrov, Appl. Catal. B 63 (2006) 266. [9] V. Iliev, D. Tomova, R. Todorovska, D. Oliver, L. Petrov, D. Todorovsky, M. Uzunova-Bujnova, Appl. Catal. A 313 (2006) 115. [10] V. Iliev, D. Tomova, L. Bilyarska, G. Tyuliev, J. Mol. Catal. A 263 (2006) 32. [11] M.A. Hasnat, M.M. Uddin, A.J.F. Sameda, S.S. Alama, S. Hossain, J. Hazard Mater. (2007), doi:10.1016/j.jhazmat.2007.01.040. [12] J. Krysa, G. Waldner, H. Mestankova, J. Jirkovsky, G. Grabner, Appl. Catal. B 64 (2006) 290. [13] I.K. Konstantinou, T.A. Albanis, Appl. Catal. B 49 (2004).

present study, it may not be possible to make some experimental restrictions over the zero order kinetics or on the LangmuirHinshelwood kinetics. However, the arguments presented herein can be applied to the experimental data and will be helpful in predicting the process theoretically. References
[1] A. Houas, H. Lachheb, M. Ksibi, E. Elaloui, C. Guillard, J.M. Hermann, Appl. Catal. B 31 (2001) 145. [2] W.Z. Tang, H. An, Chemosphere 31 (1995) 4157. [3] I.K. Konstantinou, T.A. Albanis, Appl. Catal. B 42 (2003) 319. [4] A.K. Gupta, A. Pal, C. Sahoo, Dyes Pigments 69 (2006) 224. [5] C. Sahoo, A.K. Gupta, A. Pal, Desalination 181 (2005) 91.