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Catalysis Communications 9 (2008) 82–84

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Langmuir–Hinshelwood kinetics – A theoretical study

a,*
K. Vasanth Kumar , K. Porkodi b, F. Rocha a,*

a
Departamento de Engenharia Quı́mica, 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 Langmuir–Hinshelwood kinetics to zero order
kinetics.
 2007 Elsevier B.V. All rights reserved.

Keywords: Heterogeneous catalysis; Langmuir–Hinshelwood kinetics; Theory; Zero order kinetics

Langmuir–Hinshelwood (LH) kinetics is the most com- 1 1 1

¼ þ : ð4Þ
monly used kinetic expression to explain the kinetics of the r0 k r k r KC 0
heterogeneous catalytic processes. The Langmuir–Hinshel-
wood expression that explains the kinetics of heteroge- Most of researchers approximated Eq. (1) to first order
neous catalytic systems is given by: kinetics for the condition KC  1 [1–7]. Recently, some pa-
pers reported that the LH kinetics as in Eq. (2) can be
dC k r KC approximated to zero order kinetics for KC0  1. How-
r¼ ¼ ; ð1Þ
dt 1 þ KC ever, if the LH expression is written in terms of initial reac-
where r represents the rate of reaction that changes with tion rate, for KC0  1, the Langmuir Hinshelwood kinetics
time. will not reduce to a zero order kinetics [8–12]. As a case
The term r in Eq. (1) was represented in terms of initial study, the literature data for the photocatalytic degrada-
reaction rate, r0, as a function of the initial dye concentra- tion of Eosin Y by TiO2 P25 catalyst [7] was used. Fig. 1
tion, C0, or in terms of Ce, where Ce is the equilibrium dye shows the plot of r0 versus Ce for various K values. The fig-
concentration in solution after the completion of dark ure shows the simulated r0 values using Eq. (3), for exper-
experiments. The initial rate of reaction as a function of imental values and also for increasing K values. From
C0 and Ce is given by Eqs. (2) and (3), respectively: Fig. 1, it can be observed that increasing the K values from
k r KC 0 2 to 4 times the experimental K value, the simulated r0 devi-
r0 ¼ ; ð2Þ ated much from the experimental kinetics. This shows the
1 þ KC 0
significance of the KCe in the LH expression as in Eq.
k r KC e
r0 ¼ : ð3Þ (3), and suggests that the term KCe in a Langmuir–Hinshel-
1 þ KC e wood kinetics represented in the form of initial reaction
The parameters kr and K which are a function of C0 or Ce rate should not be neglected.
can be predicted by linearizing the Eq. (2) or (3) as follows: In the case of Eq. (1), the constants kr and K can be cal-
culated from the corresponding integrated expression. This
*
Corresponding authors.
equation can be integrated between the limits: C = C0 at
E-mail addresses: vasanth_vit@yahoo.com (K.V. Kumar), frocha@ t = 0 and C = C at t = t. The integrated expression is given
fe.up.pt (F. Rocha). by:

1566-7367/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2007.05.019
 K.V. Kumar et al. / Catalysis Communications 9 (2008) 82–84 83

Notations

Ce equilibrium dye concentration in solution after kr limiting rate constant of reaction at maximum
the completion of dark experiments, mg/L coverage under the given experimental condi-
C0 initial dye concentration, mg/L tions.
C concentration at any time t during degradation, r rate of reaction, mg/L min
mg/L r0 initial rate of reaction, mg/L min
K equilibrium constant for adsorption of the sub- t contact time, min
strate onto catalyst k0 zero order reaction rate constant, min1

 
C0 used to predict the constants kr and K in the LH
ln þ KðC 0  CÞ ¼ k r Kt: ð5Þ
C expression.
In addition, for KC  1, the Langmuir–Hinshelwood
If the term KC  1 then Eq. (1) is reduced to: kinetics cannot be reduced to zero order kinetics. If the
r ¼ k r KC: ð6Þ kinetics of studied system follows zero order kinetics, then
the rate expression should be expressed as:
Integrating Eq. (6) with respect to limits: C = C0 at t = 0
and C = C at t = t, LH expression reduces to a first order dC
r¼ ¼ k0: ð7Þ
kinetics and is given by: dt
 
C Thus the rate r in Eq. (7) is not related to r or r0 as in Eq.
 ln ¼ k 1 t; (2) or Eq. (3), respectively, based on the kinetic theories be-
C0
hind these expressions. The constants kr and K should not
where k1 = krK be approximated to a single constant by ignoring the term
If the term krK  1, then the denominator of Eq. (1) KC in the denominator of the Langmuir–Hinshelwood
becomes more significant in predicting the LH kinetics. kinetics. Though the experimental kinetic data is linear,
Thus it is to be remembered that for KC  1, Eq. (1) can- the rate of reaction cannot be made equivalent to Eq. (2)
not be reduced to zero order kinetics as mentioned in some or (3), instead the rate of reaction as in Eq. (7) can be used
of referred papers [8–13]. If KC  1, then Eq. (5) is to be to approximate the experimental kinetics. Based on the

0.9

0.8

0.7

0.6 K: Experimental
ro, mg/L.min

K: 2*Experimental
0.5 K: 3*Experimental
K: 4*Experimental
0.4

0.3

0.2

0.1

0
0 20 40 60 80 100
Ce, mg/L

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 different K values in the presence of
1 g l1 TiO2 P25 [7].
84 K.V. Kumar et al. / Catalysis Communications 9 (2008) 82–84
present study, it may not be possible to make some exper-
imental restrictions over the zero order kinetics or on the
Langmuir–Hinshelwood kinetics. However, the arguments
presented herein can be applied to the experimental data
and will be helpful in predicting the process theoretically.
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