JOURNAL OF CATALYSIS 16, 1264% (1976)

NOTES

Comments on the Elovich Equation

The Elovich equation (1, 2) has been a new set of coordinates (q,t) which repre-
widely applied to chemisorpt’ion kinetics sent the chemisorption (Fig. 1)
in its integrated form:
t = t’ - to \

I
1 1
q = - ln(t + to) - - In to. (1) q = i ln t1 - 1 In to = ’
a cy CY a . (3)
Here q is the amount chemisorbed at time ln(t + to) - jJ In to
t and a! and t, are constants. The parameter )
to is chosen to linearize a plot of q against
The parameter to plays a purely mathe-
ln(t + to) and 01 is calculated from the
matical role. Claims (4) for a precise
gradient of this plot. The differentiated
physical meaning for to are of doubtful
equation is,
validity. The parameters of possible phys-
& ical significance are a and a.
- = a exp(-aq), (2)
dt Distinct breaks (2) often occur in Elo-
vich plots. If to(j) represents the to value
and a = l/&a if q = 0 at t = 0.
for a later Elovich section with a new value
Much debate exists as to the significance
of a(=(~~j,) the data are well described by
of to, a and a. Peers (3) has pointed out
Eq. (1) if (5, 6)
that t, must have a nonzero value, how-
ever small, but many authors obtain ap- tom = 00 + t’>, (4)
parently linear plots of q against In t, i.e.,
where to is the constant originally chosen
to = 0, and imply that Elovich kinetics to linearize the plot and t’ is the time for
apply from t = 0. It is worthwhile dis-
which previous Elovich section(s) have
cussing this more explicitly.
The Parameter to
Here q1 and t1 are used for curves with
to = 0. A plot of q1 = (l/a) In t1 is shown
in Fig. 1 for #a!= 0.50. A family of such
curves exists, each with a different value of
a but all passing through (ql = 0, t1 = 1).
It is apparent that not only is (dq’/dtl)
infinite at t1 = 0 but also that q1 = -m at
t1 = 0. Equations (1) and (2) have no
physical significance when to = 0 (Sj.
The value of CYis determined by which
of the family of q1 against In t1 curves ap-
plies to the kinetic process. The parameter I I
2.0 4.0 6.0 6.0 10.0 1’
t, is then concerned with the point on the
curve at which the process begins. The FIG. 1. Plot of Q’ = (l/a) ln t1 for a = 0.50
origin is shifted by t, on the time axis (and showing the significance of to in the integrated Elovich
hence by l/a In to on the q1 axis) to give equation.
126
 NOTES 127

been in force. This is confirmed if the origin a sudden change in the character of the
is shifted so that the start of a second (or surface at a particular q value. Models of
later) Elovich section becomes the point site creation (9) or of aggregation of ad-
(Q = 0, t = 0). An integrated Elovich plot sorbate (7) may be more appropriate in ex-
can then be obtained for this section in the plaining the abrupt alterations in ICY.The
usual way and the disposable parameter fact that (dq/dt) also changes abruptly is
necessary to linearize the plot turns out to of relevance here.
have a value (t, + t”) in agreement with The electronic theory (10) of catalysis
Es. (4). on semiconductors deals successfully with
There is no obvious reason why this many aspects of chemisorption on these
parameter should be related to the time solids but its application to chemisorption
for which previous Elovich section(s) have kinetics (11-14) leads to an Elovich rate
lasted. This situation indicates not only a law only in specific circumstances. Kuznet-
sharp change in the rate of decrease of sov (13) has shown that Elovich kinetics
(dq/dt) but also in (dq/dt) itself. It is should apply to the particular case of
easily verified that the rate (&/dt) at the chemisorption on a “quasi-isolated” (10)
end of an Elovich section cannot equal that semiconductor surface when the Fermi level
at the start of a following section if (Y passes near the upper boundary of the
changes in value and to(i) = (t, + t”). band edge. The kinetics should then follow:
These rates are only equal if
N= yin {exp (;I&)
to(i+l) = Q(j) (to + t*).
a(i+l)

The Parameters Q and (Y + 4sT t exp(fg + fs - .I”+ + El, - Q&J]1

The constant a represents the rate of (6)
chemisorpt’ion at the beginning of an
Elovich section. Its physical significance is where N is the amount chemisorbed at time
fairly straightforward. In certain circum- t. The symbols in Eq. (6) are defined in
stances (6, 7) its variation with tempera- Ref. (13) but comparison of Eqs. (1) and
ture may be used to calculate activation (6) shows that a = (h2/4wn”kT) where
energies for chemisorption. vz* is the effective mass of carriers in the
In chemisorption models where Elovich surface band. For chemisorption at con-
kinetics follow from an activation energy stant temperature changes in a! could only
(E) which increases linearly with coverage result from changes in w’~. It would bc
a certain physical significance can be at- tempting to equate sharp breaks in Elovich
tached to or since (2, 8) plots with abrupt changes in m.“.
It is dangerous to yield too easily to such
E(q) = B(O) + “Q, (5) temptations. Elovich kinetics apply to
where E(Q) is the activation energy at chemisorptions on a wide range of solids
coverage q. Otherwise the significance of (Y and not only on surfaces which could have
is less clear and it is loosely taken to repre- the specific characteristics described by
sent the deceleration of the uptake. Kuznetsov. It has been st’rcssed (2) that
“Breaks” in Elovich plots indicate an adherence of data to Elovich kinetics does
abrupt change in N. To account for this it not prove a particular mechanism of chcmi-
is assumed t’hat distinct sets of adsorption sorption. It has not been stressed, however,
sites exist and that each has a character- that the Elovich rate law also describes a
istic value of CY.Abrupt “breaks” are taken wide variety of reactions outside the field
to result from complete filling of the first of chemisorption. For example, such diverse
set of sit’es before significient adsorption processes as the following obey Elovich
begins on the second set. This model does kinetics: (a) the oxidation of metals (15) ;
not seem realistic. A more convincing ex- (b) the oxidation of coals and chars (16) ;
planation of abrupt changes in 01 would be (c) decomposition of surface formate on
128 NOTES

nickel (17) ; (d) decay of photoconduction (1960) ; and “The Electronic Theory of
in semiconductors (18, 19) ; (e) decay of Catalysis on Semiconductors.” Macmillan,
photogenerated free radicals in a photo- New York, 1963.

:i PESHEV, O., Russ. Chem. Rev. 35, 761 (1966).

synthetic system (20) and in melanin (21) ;
VOLKENSHTEIN, F., AND PESHEV, O., Kinetics
(f) graphitization of carbon (22) ; (g) an- ’ Catalysis (USSR) (Eng. Transl.) 6, 79
nealing of films of carbon (23) and silicon (1965).
carbide (24) ; and (h) ion transport across 13. KIJZNETSOV, V. S., Kinetics Catalysis (USSR)
cell membranes (25). A profusion of models (Eng. T~an.sZ.) 5, 471 (1964).
exists to explain Elovich kinetics in these l/t. KUZNETSOV, V. S., Kinetics Catalysis (USSR)
systems. (Eng. Transl.) 4, 772 (1963).
It would be prudent not to attribute un- 15. KUBASCHEWSKI, O., AND HOPKINS, B. E., “Oxi-
due physical significance to Elovich param- dation of Metals and Alloys.” Butterworths.
eters unless a general mechanism can be London, 1962.
suggested to take account of its widespread 16. NEWMAN, J. 0. H., STANLEY, L., EVANS, P. L..
COLDRICK, A. J. T., KEMPTON, T. J., Nature
applicability. It may turn out that the 213, 280 (1967).
Elovich equation represents only an em- lr FUKUDA, K., NAGASHIMA, S., NOTO, Y., ONISHI,
pirical approximation to actual behavior. ’ T., AND TAMARU, K., Trans. Faraday Sot.
If this is not the case it could eventually 64, 522 (1968).
prove to b,e of fundamental significance. 18. NOBBS, J. McK., Phys. Cham. Solids 29, 439
( 1968).
REFERENCES 19. PAGNIA, H., Surface Sci. 10, 239 (1968).
1. ROGISBKY, S. Z., AND ZELMIVICH, J., Acta 20. COPE, F. W., Proc. Natl. Acad. Sci. U. S. 51,
Physicochim. USSR 1, 554 (1934). 809 (1964).
2. Low, M. J. D., Chem. Rev. 60, 267 (1960). 21. COPE, F. W., J. Chem. Phys. 40, 2653 (1964).
5. PEERS, A. M., J. Catalysis 4, 672 (1965). $2, MIZUSHIMA, S., Proc. Conf. Carbon, 6th, Univ.
4. CIMIX~. A., MOLINARI, E., AND CIPOLLINI, E., Park, Penna., 1961 2, 439 (1963).
Actw Second Congr. Intern. Catalyses, 2”, 23~. MCLINTOCK, I. S., AND Oaa, J. C., unpublished
Paris 1960 1, 263 (1961). results.
5. MCLINTOCK, I. S., AND RITCHIE, M., Trans. $4. MOGAB, C. J., AND KINGERY, W. D., J. Appl.
Faraday Sot. 61, 1007 (1965). Phys. 39, 3640 (1968).
6. MCLINTOCK, I. S., Nature 216, 1204 (1967). 25. COPE, F. W., Bull. Math. Biophys. 27, 99
Y. AI.LEN, J. A., AND SCAIFE, P. H., Australian J. (1965).
(‘hem. 19, 2015 (1966).
HAYWAI~D, D. O., AND TRAPNELL, B. M. W., I. S. MCLINTOCK
“Chrmisorption.” Butterworths, London,
1964. lsotopps Laboratory
9. TAYLOR. H. A., .4x” THON, N.. J. Am. Chem. University of Dundee
Sot. 74, 4169 (1952). Dundee, Scotlwd
10. VOLKENSHTEIN, F.. Advnn. Cntnlysis 1’2, 189 Received Mny 13, 1969