Application of Kinetic Approximations

to the A 2 B -+ C Reaction System

Gregory I. Gellene
Texas Tech University, Lubbock, TX 79409-1061
Two of the most often discussed procedures for simplify-
ing the kinetic analysis of chemical reaction systems are
the steady-state (ss) and the preequilibrinm (pel assump-
tions ( I ) . The domains of applicability of these kinetic as-
sumptions as applied to the title reaction system are deter-
mined by a comparison of the exact solution of the rate
equations to the corresponding approximate solutions.
The Simple Steady State
The steady-state approximation is often introduced ( 1, 2)
by considering the consecutive first-order reaction system,
for which the corresponding coupled differential equations
can be analytically solved by elementary techniques to
yield the exact solutions.
The steady-state assumption for the reaction intermedi-
ate (i.e., d[Bl""/dt = 0) is usually applied to the special case
of [Blo = 0; however, this condition is not required. Because
the general approach for applying kinetic approximations
is not widely treated and will be used throughout, it will be
outlined here. If the steady-state equations
(where the superscript denotes the kinetic approximation
invoked) are combined with the mass-balance relationship
(which must hold for any valid kinetic approximation), a
steady-state solution can be obtained for arbitrary initial
concentrations.
Using eq 8 to eliminate [AISs from eq 10 gives upon rear-
rangement
Substitution of eq 11 into eq 9 allows [ CF to be deter-
mined by direct integration. This result allows [BY to be
determined from eq 11, which in turn allows [AIS3o be de-
termined from eq 8. The final results are
where k,, = klkz/(kl + kz).
These approximate results can be compared to the exact
solutions (eqs 5-7) to identify t he domain of applicability
of the steady-state assumption as kz>> k, (i.e., kzf k1 = kz
and h., = kl) and t >> Ilkz (i.e., e-ks' = 0 and [Clg = [Blo +
[Clo). Under these conditions the familiar steady-state so-
lutions for this reaction system are recovered. Although
this approach cannot be generalized to explore the condi-
tions under which the steady-state approximation for an
arbitrary kinetic system is valid (31, the analysis does re-
veal the two critical minimal requirements: an intermedi-
ate t hat is destroyed faster than i t is produced and suffi-
cient time for the steady state to be established.
If the reaction scheme is extended to include the reverse
of the first step of reaction 1, t hat is,
the validity of the preequilibrium assumption can be simi-
larly explored by this pedagogically satisfying approach of
comparing exact and approximate sdutions of the coupled
rate equations.
Although a numerical analysis of this kinetic system is
available (41, an analytical approach appears not to have
been explicitly treated previously ( 5) and is thus consid-
ered here. Although the solution to the more general case,
which includes the reverse of t he second step, that is,
is available (61, the rate equations for k_2= 0 case are easier
to solve and better suited for treating the preequilibrium
assumption. With apologies to those readers familiar with
t he techniques of solving elementary differential equa-
tions, some intermediate steps will be explicitly indicated
196 Journal of Chemical Education
to clarify the presentation for those with a less sophisti-
cated mathematical background.
The Exact Solution
The coupled rate equations for the title reaction system
are
which can be solved exactly by the following approach (7).
Solving eq 16 for [A1 gives
which upon substitution into eq 15 followed by differentia-
tion and rearrangement yields
This homogeneous second-order differential equation
with constant coefficients is readily solved by substitution
of the assumed solution, [BIZ e", into eq 19, which gener-
ates the characteristic equation,
having the solutions
The general solutions for [B] and [A1 now can be given as
[Bl = c+e'+' + c_er-<
1221
k,IAl = e+(r, + k., + kz)er" + c-lr- + h - ~ + kz)er-'
(23)
where the arbitrary constants, c+ and c_, can be assigned
by simultaneously solving the equations
When this is done, the exact solutions in their most sym-
metric form are given by
where eq 28 is determined by substitution of eq 27 into eq
17 followed by integration.
Approximate Solutions
Preequilibrium
The equations describing the application of the preequi-
librium approximation
k,[AIP' = k.,LBIPe (29)
combined with t he mass-balance relationship (eq 10 with
the superscript "ss" replaced by "pen), can be simultane-
ously solved by the largely algebraic approach that led to
eqs 12-14. When this is done the results are
where k,= klkz/(k-, + kJ and the familiar preequilibrium
results are recovered for [Clg' = [Clo.
Anticipating that the domain of applicability of eqs 31-
33 will require the equilibrium reactions to be fast (in a
sense to be determined) relative to the rate of C formation,
we rewrite eq 21 as
If kz << (k-1 + kl), the square root in eq 34 can be ex-
panded in powers of k ~ / ( k . ~ + kl) with the result
Neglecting terms beyond first-order in kzllk-I + k1) gives
the approximate results
( k z <c k-I+ kll 1371
Substitution of eqs 36 and 37 into eqs 26-28 yields
Acomparison of eqs 38-40 with eqs 31-33 indicates t hat
k2 << (k-, + kll together with t >> ll(k-, + kl) li.e.,
e - ~ k , + k " , = 0) is sufficient for the preequilibrium approxi-
mation to be valid. Under these conditions
Volume 72 Number 3 March 1995 197
wher e t he fi nal i nequal i t y allows [Cl o -
[CIBe to be neglected i n eqs 31-33, and t he
familiar, simple preequilibrium results are
recovered. However, if t he required condi-
tion on t he rat e constants i s only weakly sat-
isfied (i.e., k z < (k., + k l ) ) , eq 41 provides t he
first correction t erms to simple preequili-
brium results.
Because the condition of kz << (k.l+ k l ) does
not di st i ngui sh between k-I and k l , t he
preequilibrium approximation will be valid if
k z is very much smaller than one of the equi-
librium rate constants regardless of the mag-
nitude of the other equilibrium rate constant.
This point has not always been fully appreci-
ated (8). As was the case with the steady-state
approximation, i t is not possible to determine
the validity of the preequilibrium approxima-
tion for an arbitrarv kinetic system. Neverthe-
Table 1. Results of Applying Kinetic Approximations
to the Reaction System
kl k2
+
A-B-c
k-1
Required conditions k2 << (kr + kr)
kr << (k-1 + kz)
Induction time t>> l / l kr +XI ) t>> I4k.r + k2)
Effective rate constant
= kik*(k.~ + k ~ ) kss = krkz4kr + k2)
less, this analysis does identify the two essen-
tial requirements of a reaction equilibrium
having either a forward or a reverse rate t hat
is large compared to the rate of species removal from the
equilibrium and the passage of sufficient time for the equi-
librium to be established. The results are summarized i n
the second column of Table 1.
Steady State
Preequilibrim Steady State
It is also of interest to apply the steady-state approxima-
tion (d[B]"ldt = 0 ) to the title reaction system so that the
results can be compared with those of the preequilibrium
nppr<rximation hi iipproxh proceeds in the manner out-
l ~ned in the t r wt n~ent ol'the simple: cteadv-state with the
exception t hat eq 8 is replaced b;
k,lAl" = (k-I + kz)[BlsS ( 42)
The resulting solutions are
where kss = k l k z / ( k ~ , + k l + k z ) . With the expectation that
the validity of the steady-state approximation will require
k l << k _ l + k z (for which kss = kl kZ/ ( k- , + k z ) ) , eq 21 is re-
written as
Proceeding as before yields the results to first order in
k ~ / ( k . ~ + kz ) .
Substitution of eqs 47 and 4 8 into eqs 26-28 yields
Acornparison of eqs 49-51 with eqs 4 3 4 5 indicates t hat
k , << (k., + k,)
together with
t >> ll(k-, + kzl
(i.e., e-lk~' + k' ' ' = 0) is sufficient for t he steady-state approxi-
mation to be valid. Under these conditions
[CI; = [Clo + kz[Blo/ik-l+ kz)
The final results are listed i n the third column of Table
1. As before, the validity of the steady-state approximation
requires t hat the intermediate be consumed faster than i t
is created (kl << k., + k z ) and that the steady-state he es-
tablished (t >> l l ( k- l + kz) ) .
Concluding Remarks
A comparison of the exact solution of the kinetic system
to the approximate solutions obtained under the assump-
tions of preequilibrium and steady-state indicate that the
preequilibrium assumption is valid for k z << (k-, + k l ) and
t >> l I ( k- , + k, ) , whereas the steady-state assumption is
valid for k 1 << + k z ) and t >> l i ( k - ~ + kz ) .
198 Journal of Chemical Education
These conditions are not mutually
Table 2. Relative Magnitudes of ki, kl, k2 Required for the Validity of the
exclusive. For example, both kinetic
Pre-equilibrium (pe) and Steady-State (ss) Kinetic Approximations
assumpt i ons ar e simultaneously
valid under the conditions k l << kz
Relative induction time Valid approximation Rate-Controlling stepa
<< k- ] and t >> V(k.l + k l ) as can be
seen readily by noting that eq 42 re- k, .. k, << k2 t>> 14111 1 k) ss 1
duces to eq 29 under these condi-
tions. Less obvious, perhaps, is that
kl << k2 << kl t>> l 4l ct + k,) pe 2
the two kinetic assumptions are also
k~ << h2<< h-1 t>> l/(h., +kt ) ss and pe 2
simultaneously valid for the condi- k, << k-, << h2 t>> I/(~.I + h2) ss I
tions k2<< k1 << k- ] and t >> l l ( k . l +
h2<< h_l << hl
k 2 ) . The six possible orderings of the
magnitudes of k.l, k l , and k2 are con-
<<hl<< h-1
sidered in Table 2 where the valid
'Reference 9.
kinetic approximations ar e indi-
cated. Also. i t bas been noted (9). t hat when the maenitude
of all thred rate constants are considerably different, the
reaction svstem has a rate-controlline steD indicated in the
last colu& of Table 2. It is hoped t f a t t i ese comparisons
provide some clarification of the complementary and some-
times overlapping roles of the steady-state and preequili-
brium approximations in t he solution of chemical rate
equations.
Literature Cited
1. See. for ~xample. Atkins. P. E. Phyricoi Ch~rnislqv, 4th ed.: Freeman: New York, 1990:
PP 800402.
2. Hammes. G. G . ; P r i ~ z ~ i ~ i e ~ ~ f C h ~ m i m l K~ndics;Academic: NewYork, 1978, pp 10-11.
3. Laidler. K. J. Chmzicoi Kinr!i~s. 3rd ed.: Harper New York. 1987; p 2R2.
4. Volk, L.: Richardson. W.: Lau. K. H.: Hall. M. ; Lin. S. H. J. Chem. Wa c . 1977, 5495.
5. Although the exset and approximate sol"fions am glven by Moore. J. W: Pearson. R.
G. Ki nl i cr and MpchnnLvn 3rd ed.: Wiley: NewYork, 1981: pp 313-315, the rela-
tionship between them is not developed.
Acknowledgment
fi. Lnwery.T. M.; John. W. T J Chenl. Sm. 1910. 97. 2634.
7 . Boyee. W. E. : DiPlima. R. C. Elcmnrlor:" Di/firn,li"i Epiralio,,~ "lid Bou,,dnin,>, vn1r.c
I thank the National Science Foundation (Grant C H E 9 O -
~ ~ ~ h l ~ , ~ ~ . 3id ed.; witey: N ~ W Y W~ , 1977: p 272.
2 4 0 9 1 ) and the Research Enhancement Fund of Texas Tech
8. ~ e v i ne . I . N ~ h ~ s i c n i ch~mi r t r y, 3rd. ed.; M C G ~ W - H ~ I I : ~ e w ~ o r k , 1988: p 530.
University for partial support of this research. 9. ~ ~ i d k K J. J C I L ~ Z . E ~ U C 1988, 6s. 250.
Volume 72 Number 3 March 1995 199