L. Volk, W.

Richardson,
K. H. Lau, M. Hall,
I
Steady State and Equilibrium
and S. H. Linl
Arizona State University
Temp. 85281
Approximations in Reaction Kinetics
In the kinetics of complex reactions, the steady state and
equilibrium approximations are often used (I ). However, little
has been done to investigate the validity of these approxi-
mations on quantitative terms. I t is the purpose of this paper
to study the limitation of the application of these approxi-
mations to the kinetics of complex reactions. For this purpose,
we shall study the following two types of reactions
kc bz
A e B- C
* .
..-.
The reason for choosing these reactions is to investigate how
the reversible reaction affects the applicability of the steady
state approximation.
Reactlon (1)
To describe the approach we adopt in discussing the validity
of the steady state approximation or equilibrium approxi-
mation, we shall go through reaction (1) rather in detail, al-
though most of the results are well known. The rate equations
for this case are given by
-- dA - - kl A
dt
-- dB - kl A - k2B
dt
-- dC - kzB
dt
(3)
and the exact solutions of these equations based on the use
of the initial conditions A = Ao, B = C = 0 can he written
and
B = k l A o ( e - b , t - e- k2t )
kz - k ,
( 5)
Notice that A + B + C = Ao
In order to test the validity of the steady state approxima-
tion as applied to B, we compare the exact expression for the
rate equation for C with the approximate rate equation for C
obtained from the use of the steady state approximation,
i.e.
- kn [I - e-,b2-k,)t]
D(ki , t ) =--
k, A k 2 - k ,
(6)
The factor D may be regarded as representing the extent of
deviation for the steady state approximation. In other words,
the factor D may be used to test the performance of the steady
state approximation. However, it should be noted that this is
not the only way to study the validity of the steady state ap-
proximation. It is useful to consider the time required for the
steady state to he reached. If we let the time at which the
concentration of B is a maximum be denoted by t., then an
explicit expression fort, can be obtained from setting dBldt
= 0, i.e.
t , = -
kz
log-
k z - k ~ k~
(7)
At t = t,, D = 1. That is, at this point the steady state ap-
proximation holds exactly.
For the purpose of numerical comparison, it is convenient
John Guggenheim Fellow.
. ; : I 3
.;:2.
..,.
I i I I 1 I I I
2 4 6 8 10 12 I4 16
ati
Figurn 1. Plot of Dverrus At' far various k2'.
I i I I I i I I
5 10 15 2 0 2 5 30
Izf
Figure 2. Plot of ts' versus ke'.
to use aset of dimensionlessvariables defined by kz* = k d k ~
t* = kit, and B* = B/Ao. In terms of these dimensionless
variables. we have
and
t.* = L l o g kz*
k2* - 1
(9)
where At* = t* - t,'. When t* - m, eqn. (8) reduces to
k *
D(kz*, m) =A
kz* - 1
(10)
Both eqns. (8) and (10) indicate that the steady state ap-
proximation is valid when k2* >> 1 or kz >>k, . In other words,
for reaction (I), the steady state approximation holds under
the condition in which the intermediate B disappears quickly
once it is formed.
Figure I is a plot of D versus At' for various kz*, where At*
denotes the time after which 1,' has been reached. The upper
Volume 54, Number 2, February 1977 1 95
limit for each curve is kz*lkz' - 1, while the lower limit is D
= 1. The distance from the D = 1 line to each D versus At*
curve gives the deviation involved in the steady state ap-
proximation for a particular k2* value. For example, for the
steady state approximation to hold within 5%, i t is required
that kz* > 20 (cf. eqn. (10)). Figure 2 shows a plot oft.* versus
kzl; i.e., it shows how rapidly the steady state is reached under
various conditions. Sometimes it is important to estimate the
relative magnitude of the intermediate B relative to A, i.e., to
see if the reaction intermediate is detectable. For this purpose,
it should he noted that BIA = Dlkz', which indicates that
under the condition in which the steady state approximation
is valid, the concentration of B is very small.
Suppose we require the steady state approximation t o be
valid within 1% (i.e., 0.99 5 D _< 1.01). In this case, from eqn.
(10) andD = 1.01, we can determine kz* to be kzt = 101, and
from eqn. (a), k2* = 101 andD = 0.99, we obtain the time t ~ *
= log 101/2/100 after which the steady state approximation
will he valid within 1%. tw* should be compared with t.' = log
1011100. It should be noted that the maximum concentration
of the intermediate I3 can he calculated easily by setting dBldt
= 0 to obtainlog B,/Ao = -kz*l(kz* - 1) log &*.In this case,
we have B,I& = (101)-1.0'. Notice that at t ~ * , A* is equal
to exp (-(11100) log (10112)) or 0.962. In other words, in this
case, the extent of reaction is quite small (-4%). Similarly,
suppose if we require the steady state approximation to be
valid within 0.1%, then BJAo = (lOO1)-l.W1 and at t ~ * , A*
is equal to exp (-(111000) log (100112)). In this case, the extent
of reaction is less than 1%.
Readlon (2)
Reaction (2) corresponds to the Lindemann scheme and
much bas been discussed about this mechanism ( 24) . This
is a tint-order consecutive reaction with a reversible fmt step;
the rate equations are
-- dA - -klA + kLIB
dt
-- dB - k, A - k-,B - k2B
dt
-- ;: - kzB (11)
~..
Either the l.apla(wtransform or the matrix method ran be
aonlied to solve ean. (11) exactlv: the resulting dimensionless
where
A,* = %(l + k-I' + kz* + d ( 1 + k-,* + k2*)2 - 4k2*)
and
with A* = AIAo, B* = B/Ao, and t* = klt. Here i t is assumed
that at t = 0, B = C = 0. For reaction (2), both steady state and
equilibrium approximations can be applied.
Applying steady state approximation to B (i.e., dB/dt = O),
eqn. (11) is reduced to
B..* =
A*
k_, * + k2*
(16)
and dCldt becomes
dC* -
-- kz* A'
dt' kL,* + k?*
(17)
Following the discussion for reaction (1) the deviation ex-
pression D,, can he obtained from eqns. (16) and (17) as
D,(kis, t*) = (k-,* + k2*)B*IA* (18)
where B* and A* are given in eqns. (12) and (13), respectively.
When t* approaches infinity, eqn. (18) reduces to
. ..-.
The expression for ts* can he obtained from applying the
condition dBldt = 0 to eqn. (13)
t.' = log (A**/A,*)/(Xz* - A,*) (20)
Assuming equilibrium between the reactant A and the in-
termediate B, i.e., the equilibrium approximation, we have
B.,lA = kllk-,
dC*
(-1 = X A .
dt* . s k-l*
and
De,(ki*t*) = k-l*B*IA* (23)
From eqns. (23) and (la), D., is related to D,, by
kL,*
D,,(ki', t*) =
k..,* + k2*
Ddki *, t *) (24)
The limiting form of D., is given hy
D.,(k,*, m) = 1 - X2* (25)
Plots of D, versus t* and Dq versus t * are shown in Figure
3 and 4, respectively. Both plots are based on values of the
ratio k~*l k- ~' larger than and smaller than one. From Figure
3, we see that for k ~* l k - ~* < 1, the smaller the value of kz*l
k-I*, the better the steady state approximation and for
kz*lk-,* > 1, the larger value of k ~* l k - ~* gives a better ap-
proximation. Figure 4 shows that kz*lk-I* < 1 the equilibrium
approximation improves with decreasing kzxlk-I* and for
k2*lk-'* > 1, the equilibrium approximation does not apply
(see also eqn. (24)). The plot of B*IAx versus t* is shown in
Figure 3. Plat at D,, vsrsus t'
o v I I 1 I
0 05 1.9 1.5 2.0 25 3.0 35 4.0
tX(k,xt)
Figure 4. Plot at D, versus t'.
96 I Journal of Chemical Education
c
Figure 6. Plot of 1 , ' versus k2' .
Figure 5. In a previous paper ( 6) we have applied the singular
perturbation method7 to solve the Lindemann scheme and
investigate the validity of the steady state and equilibrium
approximations analytically.
Plot oft.* versus k9* with k-T* varied from 0.1-35 is shown
in Figure 6: From thisplot, one can see that at small values of
k-< * and k9'. the svstem needs loneer time to reach the steady
sta'te, as fo;the cases in which the Geady state approximation
applies (cf Figure 3), t,* may roughly be regarded as the
minimum time required for reaching the steady state. In
general, the larger the value of kz*, the shorter the time for the
system to reach the steady state. In Figure 7 the plot of kz*
versus k- ~* at D,.(ki*, m) = 1.01 (eqn. (19)) is obtained as a
limiting curve. Any combination of k2* and k-I* outside the
region bounded by this curve will give a Ddki *, m) value
within the range of 1.01 and 0.99. For practical use the time
contour lines at t " = 0.10,0.15,0.2, and 0.25 are calculated
from eqn. (18) for the values of D,.(ki*, t*) which are in the
range of 0.99 and 1.01, and plotted in the same figure. With
these contour lines the minimum time required for the system
to reach the steady state within f 1% approximation can he
determined from this figure. For example, points B and C give
aD,, value of 0.99 at t* = 0.15, but as t * approaches infinity,
they give D,, values of 1.009 and 1.003, respectively (cf. eqn.
(19)). All combinations of kz* and k-I" above the region
bounded by the limiting curve and contour t * lines represent
the cases in which the system will reach the steady state within
f 1% approximation.
K: I
Figure 7. Plot of k2' versus k-,' for steady state approximation.
el
Figure 8. Plat of k2' versus k-,* for equilibrium approximation.
A similar plot for the equilibrium approximation is shown
in Figure 8. The contour t* lines are calculated from eqn. (24)
at the values of t * = 0.08,0.12,0.20, and 0.50, and plotted in
the same figure. The behavior of the plot shown in Figure 8,
is similar to that mentioned in the steady state approximation
case. I t should be noted that D,, at time infinity cannot take
.values smaller than unity (cf. eqn. (19)), while D., at time
infinity cannot exceed unity.
Let us estimate the extent of reaction under the condition
in which the steady state approximation is valid within 1%.
From Figure 7 at t* = 0.15, k-I* = 26.0 and k2* = 2.38 (cor-
responding to point C), we find A* = 0.952, at t* = 0.15, k - ~*
= 20.0 and kz* = 6.00 (corresponding to point B), we find A*
= 0.918 and at t* = 0.10, k-]* = 30.0and kz* = 10.9, we find
A* = 0.943. In other words, at the minimum time required for
reaching the steady state the extent of reaction is small.
Similar conclusions can be reached for the case of the equi-
librium approximation.
Literature Clted
( I ) Weston, Jr.. R.. and Schwsrz, H. A,. "Chemical Kinetics." P~entice-Hall. Engleawd
Cliffs. New Jersey. 1972. pp. 17-20.
12) Pwn. C. W., J. CHEM. EDUC.. 48,196 119711.
1.. L ~ U , K. H., vdk, L., ~ichardson, W., and Eyring. H..Proc. Natl. Acod. Sci. iSi Lin.s. I
l1.S. 69,2778 (19721.
(41 Shin,H. K.,end Gidding8.J. C., J. Phys. Chem., 65.1164 11961).
( 5 ) Jachimow~ki, C. J.. and Russoll, M. E., Z Physik. Chem.. 48,102 119661.
(81 Richardson, W.. Yolk, L.. Lau, K. H.. Lin. S. H.. and Eyring. H., h c . Nnfl. Acod Sci.
0s.. 70,588 (1973).
(7) Van Dyke, M. D.. "Perturbation Method in Fluid Mochsnira,"Acsdemic Press, New
Ywk, 1964,Brsu,C.A.,J. Cham Phys., 47,1153 lL9671.
Volume 54. Number 2 February 1977 1 97