Research: Science & Education

How Does the Gibbs Free Energy Evolve in a System

Undergoing Coupled Competitive Reactions?
Ludovic Jullien*
Département de Chimie, URA 1679, Ecole Normale Supérieure, 24, rue Lhomond, F-75231 Paris 05, France

Anna Proust
Laboratoire de Chimie des Métaux de Transition, URA 419, Université Pierre et Marie Curie, 4, Place Jussieu, Casier 42,
F-75252 Paris Cedex 05, France

Jean-Christophe Le Menn
Lycée de Kerichen, rue du Prince de Joinville, F-29200 Brest, France

At constant temperature and pressure, a system spon-
taneously evolves to minimize its Gibbs free energy, G. For
a process involving a single degree of advancement, ξ, such
as an isomerization, this behavior is classically illustrated
by a trajectory down-hill on the G(ξ) curve (1). Despite its
instructional value, the more complicated case of a system
undergoing two independent reactive processes involving
two degrees of freedom has never been analyzed in this
Journal. The present paper will address two issues. First,
the meaning of kinetic/thermodynamic controls and kinetic
stability will be thoroughly revisited and illustrated. Sec-
ond, as an original contribution, we will show how the Gibbs
free energy of a reacting system varies when successively
submitted to kinetic and then thermodynamic controls.
The reaction product P1 is assumed to be less stable
than the product P2 and its formation is assumed to involve
a lower activation energy, Ea. The reasoning is usually based
on the dependence of the Maxwell–Boltzmann distribution
of kinetic energies upon the temperature (3).
Kinetic Control
By considering that the potential energies of the prod-
ucts P1 and P2 are much lower than that of the reactant R,
one has Ea1 << Ea
1 and Ea2 << Ea
2. Consequently, at low tem-
perature, one neglects the fraction of molecules having a
kinetic energy high enough to recross the barrier from prod-
ucts to reactants. This is equivalent to considering the sim-
plified kinetic scheme

Kinetic Control, Thermodynamic Control, Kinetic Stability

In many organic reactions, the competitive formation
of side-products is a common, although unwanted, phenom- (2)
enon. It is often desirable to optimize the reaction condi-
tions to maximize selectivity. Among the parameters avail-
able to adjust the selectivity, temperature is probably the
most popular. Work at low temperature is generally associ- Under these conditions, the ratio [P1]/[P2] is deter-
ated with the idea of high selectivity; this is commonly ex- mined only by the activation barriers and the application
pressed as “kinetic control”. Conversely, work at high tem- of the Eyring relation linking the kinetic constants and the
perature is generally associated with low selectivities and is standard Gibbs free energies of activation ∆rGi0≠:
often negatively expressed as being under “thermodynamic 0≠
control”. In favorable cases, a temperature change does in- ∆G
k i = kT exp
r i
duce large changes in selectivity (2). Unfortunately, this h RT
empirical observation commonly focuses attention on tem-
perature when one is attempting to rationalize the selec- eventually yields
tivity behavior and leads to consideration of this parameter
as crucial to tuning the nature of the reaction control. 0≠ 0≠
P1 k ∆rG 1 – ∆rG 2
The simple competitive reaction sequence = 1 = exp
(3)
P2 k 2 RT

Thermodynamic Control
(1) At high temperature, the available thermal energy is
considered to be large enough to assume the energy barri-
ers are easily crossed. Consequently, the thermodynamic
equilibrium is reached and the ratio [P1]/[P2] is now deter-
will be used herein to correct this misconception. In this mined by the relative stabilities of the products P1 and P2:
scheme, all steps are considered as elementary and are as-
sumed to be first-order (kinetic constants ki). At t = 0, the sys- 0 0
tem is assumed to contain only R at the concentration [R]0. P1 K1 ∆rG 1 – ∆rG 2
= = exp
(4)
The Misuse of Energy Diagrams in Discussing the Nature P2 K2 RT
of Reaction Control
where the Ki and the ∆rGi0 respectively designate the equi-
A discussion on the significance of temperature to ra-
librium constants and the standard reaction Gibbs function
tionalize the inversion of selectivity is generally based on en-
for the pathway i (1).
ergy diagrams such as those displayed in Figures 1a and 1b.
As has been emphasized in this Journal (4), although
*Corresponding author.
it provides correct values of [P1]/[P2] in the regimes of both

194 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu

 Research: Science & Education

Potential Energy The system asymptotically evolves towards the steady

G° T2
state with a characteristic time 1/(k1 + k2):
T1
Ea ∆ rG 2 °
Ea1 2

∆ rG 1 °
[R] ≈ 0
Ea
-1
Ea R
-2

∆ rG 1° k1 R 0
P1 ∆ rG 2 ° P1 ≈
k1 + k2
Reaction coordinate 1 Reaction coordinate 2 P2
a b

Figure 1. Energy diagrams associated with scheme 1 to illustrate k2 R 0

the kinetic or thermodynamic control of reaction. a: Potential en- P2 ≈
ergy as a function of the two independent reaction coordinates
k1 + k2
associated with the pathways 1 and 2. Ea represents the activa-
tion energy of the pathway under consideration. b: Horizontally In the course of this regime, eq 3 is satisfied:
expanded representation of the standard Gibbs free energies of
the reactant R, the products P1 and P2, and the transition states P1 k1
=
T1 and T2. ∆rG° and ∆rG°≠ respectively designate the standard P2 k2
Gibbs function and the standard Gibbs free energy of activation
for each reaction pathway. After a delay t1 it becomes impossible to neglect the
kinetic and thermodynamic controls, the preceding reasoning processes yielding to the formation of R, and after a delay
is not satisfactory. In particular, such a presentation could t2 the composition of the system is virtually invariant; t1 and
delude one into believing that temperature favors one path- t2 are the limits of the regime of intermediate times. These
way to the exclusion of the other. In fact, even at low tem- times can be evaluated from the eigenvalues calculated
perature, the regime of thermodynamic control is reached from the determinant of eqs 5–7. They are respectively
after sufficient delay. Thus, time emerges as an essential equal to λ0 = 0, λ1, and λ2, with:
parameter in determining the nature of the regime under
which any reaction is controlled. – k 1 + k 2 + k
1 + k
2
Characteristic Times τ1 and τ2 Govern Evolution of the λ1 =
2
Reacting System and Delineate the Extent of Kinetic and
Thermodynamic Control 2
The concentrations [R], [P1], [P2], the kinetic constants k 1 + k 2 + k
1 + k
2 – 4 k 1k
2 + k
1k
2 + k
1k 2
ki, and the formation rates of the species R, P1, and P2 are –
related by the following system of differential equations: 2

dR
=
k 1 + k 2 R + k
1 P1 + k
2 P2 (5)
dt – k 1 + k 2 + k
1 + k
2
λ2 =
d P1 2
= k 1 R – k
1 P1 (6)
dt 2
k 1 + k 2 + k
1 + k
2 – 4 k 1k
2 + k
1k
2 + k
1k 2
d P2 +
2
= k 2 R – k
2 P2 (7)
dt
Instead of directly solving the preceding set of equations, The eigenvalues λ1 and λ2 being negative,
1/ λ1 and
1/ λ2
it is both more intuitive and more chemically instructive to can be identified with two relaxation times τ1 and τ2. Intro-
proceed by approximations, to emphasize the different ki- duction of the eigenvalues into eqs 5–7 together with the
netic regimes appearing during the evolution of the reacting initial conditions provides the final solutions:
system. Hence, a regime at short times, a regime at interme-
diate times, and a regime of equilibrium can be identified.
At short times, processes that form R can be neglected k
1k
2 k
2 + λ1 k
1 + λ1 λ t k
1 + λ2 k
2 + λ2
with respect to those causing its disappearance. This is R = R + e 1 + e λ2t (11)
0 λ1λ2 λ1 λ1 – λ2 λ2 λ2 – λ1
equivalent to reducing the kinetic scheme in eq 1 to the ki-
netic scheme in eq 2. In this regime, the concentration ex-
pressions are easily derived.

R = R 0e
k 1 +k 2 t
(8) k 1k
2 k 1 k
2 + λ1 λ t k 1 k
2 + λ2 λ t
P1 = R + e 1 + e 2 (12)
0 λ1λ2 λ λ – λ λ2 λ2 – λ1
1 1 2
k1 R
P1 = 0
1 – e
k1+ k2 t
(9)
k1 + k2
k
1k 2 k 2 k
1 + λ1 λ t k 2 k
1 + λ2 λ t
k2 R P2 = R + e 1 + e 2 (13)
1 – e
λ1λ2 λ λ – λ
0 k1+ k2 t 0
P2 = (10) 1 1 2 λ2 λ2 – λ1
k1 + k2

JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education 195

Research: Science & Education

After an infinite delay, the regime of equilibrium is governs the shapes of the [P1](t) and [P2](t) curves (see Fig.
eventually reached. One has 4). τ1 constitutes a satisfactory order of magnitude for t1.
Figure 4 displays the evolution of the relative concen-
d R d P1 d P2 trations [A j ]/[R]0 (A j = R, P1, and P2) exactly calculated (eqs
= = =0 11–13) on a time scale larger than in Figure 3. The second
dt dt dt
relaxation time τ2 is graphically expressed and corresponds
to the evolution from the quasi steady state toward the
R 0 equilibrium. The three successive regimes are clearly seen.
R =
∞ 1 + K1 + K2 Thermodynamic control can then be identified as the regime
of equilibrium that occurs at times beyond τ2. τ2 thus consti-
tutes a good estimate of t2. In the present example, one says
K1 R 0 that P1 is kinetically stable in the time range [0; t2] to express
P1 =
∞ 1 + K1 + K2 that it is overrepresented in the system if compared to its
true thermodynamic stability. More generally, the concept
of kinetic stability is related to any kinetically induced de-
K2 R 0 viation from the composition at thermodynamic equilibrium.
P2 =
∞ 1 + K1 + K2 Time, not Temperature, Determines the Nature of the
Reaction Control
and eq 4 is satisfied:
The preceding calculations demonstrate that it is pos-
P1 sible to modulate the selectivity of the reaction by varying
∞ K1
= the instant t of observation (e. g., the time of reaction workup).
P2 K2 If t is on the order of t1, the concentrations of the reactants
∞
will be close to their equilibrium values and the major prod-
A nice illustration of kinetic scheme 1 (eq 1) is pro- uct will correspond to the reactive channel of lower activa-
vided by the hydrogenation of the Vaska-type complex tion energy (kinetic control). However, if t is larger than t2,
[IrBr(CO)(dppe)] (5) (Fig. 2). This example will be used to the most stable product will be obtained (thermodynamic
illustrate the present purpose. Literature data have been control). In practice, in view of the constraints exerted on
used to derive kinetic constants (see Appendix 1). human time scales, temperature has been used almost uni-
Figure 3 displays the evolution of the relative concen- versally as the parameter to “determine” the nature of the
trations [A j ]/[R]0 (A j = R, P1, and P2) either upon approxi- reaction control. In fact, changing the temperature modifies
mation of “short” times (eqs 8–10) or resulting from the rig- ki , thus displacing the characteristic times τ1 and τ2 and con-
orous solving of eqs 5–7 (eqs 11–13). Figure 3 shows that sequently the borders t1 and t2. The significance of tempera-
the approximation of short times is quite satisfactory up to ture on the regime of reactivity control can be obtained from
the times close to τ1. Moreover, [R] drops to its equilibrium derivation of the Eyring relation:
value (almost zero in the present case) after a few τ1. A 0≠
quasi-steady state is then reached, as can be seen from the ∂ ln k = ∆rH + RT
constant values of the concentrations on the time scale of the 2
(14)
∂T RT
representation. The kinetic control of the reaction is pre-
cisely identified with this regime of short times. Whereas its If one assumes that the activation enthalpy of the reaction
lower limit is unambiguously equal to 0, its upper limit t1 is remains constant in the domain of temperatures under con-
less easily defined. Indeed, the determination of t1 depends sideration, ki and thus τ1 and τ2 can be easily calculated at
on the accepted deviation of the approximate solution from the each temperature. This can be applied to the isomerization
exact one and also on the distance between τ1 and τ2, which of the Vaska-type complex [IrBr(CO)(dppe)]. Experimental

H
Br P
Ir Pathway 1
H P
CO

P1
Br P
Ir + H2
OC P

R
H
H P
Ir Pathway 2
OC P
Br

P2

P PPh2 Figure 3. Evolution of the relative concentrations [Aj]/[R]0 (Aj = R, P1,

= dppe = Ph P
P 2 and P2) either upon approximation of short times (eqs 8–10; lines)
or resulting from solving eqs 5–7 (eqs 11–13; markers) on short
Figure 2. Hydrogenation reactions of the Vaska-type complex time scales. The following kinetic constants were used: k1 = 3.5
[IrBr(CO) (dppe)]. min
1; k2 = 0.32 min
1; k
1 = 6.9 × 10
2 min
1; k
2 = 1.8 × 10
4 min
1.

196 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu


data can be used to estimate all ∆ r Hi0≠ to be roughly identical
and equal to 100 kJ mol
1 (see Appendix 2). Figure 5 displays
the evolution of τ1 and τ2 as a function of temperature. For
example, if one considers that the observation of the system
will be made after one minute, one sees that the reaction
will be under kinetic control below 288 K, under thermody-
namic control above 340 K, and in the regime of intermedi-
ate times between 288 and 340 K. More generally, in organic
chemistry, since activation enthalpies are positive and the
typical duration of reactants–products contact is on the order
of hours, reactions under kinetic control are performed at
low temperature (
100 to
20 °C), whereas reactions under
thermodynamic control are conducted at high temperature
(60 to 150 °C).
Figure 4. Evolution of the relative concentrations [Aj]/ [R]0 (A j = P1
and P2) resulting from solving eqs 5–7 (eqs 11–13). The arrow
represents the domain of kinetic stability. The following kinetic con-
stants were used: k1 = 3.5 min
1; k2 = 0.32 min
1; k
1 = 6.9 × 10
2 min
1;
k
2 = 1.8 × 10
4 min
1.
Figure 5. Evolution of τ1 and τ2 as a function of temperature for
the Vaska-type complex [IrBr(CO)(dppe)]. The following kinetic
constants were used: k1 = 3.5 min
1; k2 = 0.32 min
1; k
1 = 6.9 × 10
2
min
1; k
2 = 1.8 × 10
4 min
1. The standard activation enthalpy was
taken equal to 100 kJ mol
1 for all processes 1,
1, 2, and
2.
JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education
Research: Science & Education
Evolution of the Gibbs Free Energy in a System
Involved in Competing Equilibria
When considering Figure 4, students are often puzzled
with the non-monotonic evolution of the [P1] concentration.
As is the case for oscillating reactions, the evolution prin-
ciple arising from thermodynamics is soon questioned. We
will demonstrate how the Gibbs free energy evolves for a
reacting system that obeys eq 1. In the case presented in
the preceding paragraph, the Gibbs free energy of the sys-
tem is a function of two independent advancements, ξ1 and
ξ2, defined by
dnP1 = dξ1
dnP2 = dξ2
dnR =
d(ξ1 + ξ2)
where the nAj represents the amount of the A j species ex-
pressed in moles. Setting
Σj n Aj = 1
the advancements ξi can be identified with the relative con-
centrations [Pi]/[R]0 obtained in the preceding paragraph
(eqs 11–13). Under assumption of an ideal solution, the mo-
lar Gibbs free energy g(ξ1, ξ2) of the reacting system at con-
stant temperature and pressure can therefore be written:
g ξ1,ξ2 = 1 – ξ1 – ξ2 µR T,P,ξ1 = 0, ξ2 = 0 + RT ln 1 – ξ1 – ξ2
+ ξ1 µP T,P,ξ1 = 1, ξ2 = 0 + RT ln ξ1 (15)
1
+ ξ2 µP T,P,ξ1 = 0, ξ2 = 1 + RT ln ξ2
2
Arbitrarily choosing the value of µR(T,P,ξ1 = 0, ξ2 = 0) to be
zero, the preceding expression becomes
g ξ1,ξ2 ξ1 ξ
= 1 – ξ1 – ξ2 ln 1 – ξ1 – ξ2 + ξ1 ln + ξ2 ln 2 (16)
RT K1 K2
Figure 6 displays the evolution of g(ξ1,ξ2) as a function
of time t by introducing ξ1 and ξ2 as extracted from eqs 12–-
13 into eq 16 for the previous example. It demonstrates that
g(ξ1,ξ2) is a monotonically decreasing function of time even
though the second term of eq 16 evolves non-monotonically.
Thus, the Gibbs free energy of the system continuously drops
in the course of the evolution and consequently satisfies the
dG < 0 criterion. The g(ξ1,ξ2)(t) function also exhibits the
two characteristic times associated with the evolution.
Figure 7a is a three-dimensional representation of the
reaction trajectory during hydrogenation of the Vaska-type
complex [IrBr(CO)(dppe)] as a function of ξ1 and ξ2. Figures
7b, c, and d show respectively the projection of Figure 7a on
the (ξ1,ξ2), (g(ξ1,ξ2),ξ1), and (g(ξ1,ξ2),ξ2) planes.
In Figure 7a, the reaction trajectory does not follow the
curve of largest slope of the g(ξ1,ξ2) surface as one might
expect. The trajectory is in fact totally determined by the
mechanistic pathways (here expressed by the ki kinetic con-
stants). Indeed, whereas a linear relation between kinetic
rates for forward and reverse reactions and the reaction af-
finity can be derived close to the position of a chemical equi-
197
 Research: Science & Education

Figure 6. Evolution of molar Gibbs free energy g (ξ1,ξ2) as a function

of time t. The following kinetic constants were used: k1 = 3.5 min
1;
k2 = 0.32 min
1; k
1 = 6.9 × 10
2 min
1; k
2 = 1.8 × 10
4 min
1.

librium (6), it does not hold far from equilibria so as to sat-

isfactorily account for the whole trajectory describing the
intermediate evolution.
The reaction trajectory clearly exhibits the two regimes Figure 7. a: Three-dimensional representation of reaction trajectory
of evolution (Fig. 7b): corresponding to evolution during hydrogenation of the Vaska-type
1. Toward the quasi steady state S. It is a portion of complex [IrBr(CO)(dppe)] as a function of ξ1 and ξ2. b–c: Projections
straight line with a slope equal to k2/k1. Both reaction of Fig. 7a on the (b) (ξ1,ξ2), (c) (g(ξ1,ξ2), ξ1), and (d) (g(ξ1,ξ2), ξ2)
products are obtained at a constant ratio. This regime planes. The following kinetic constants were used: k1 =3.5 min
1;
continues until the near depletion of reactant R. At
k2 = 0.32 min-1; k
1 = 6.9×10
2 min
1; k
2 = 1.8×10-4 min
1.
this stage ξ1 + ξ2 ≈ 1.
2. Then towards equilibrium E. It is a portion of the
straight line of equation ξ1 + ξ2 = 1 resulting from the
quantitative transformation of P1 into P2. It stops at
the point representing the equilibrium.

Eventually, although g(ξ1,ξ2) appears in a one-to-one

relation with each couple (ξ1,ξ2) on the reaction trajectory,
Figure 7c shows that the same value of ξ1 may correspond
to two different values of g(ξ1,ξ2). This does not indicate any
bistability but manifests the independence of both advance-
ments, ξ1 and ξ2.
This example illustrates the evolution of a system sub-
mitted to coupled reactions (7): at constant pressure and
temperature, the derivative of eq 15 versus time provides
the following relation:
a b
dg dξ dξ
= ∆r g 1 1 + ∆r g 2 2 (17)
dt dt dt
where the ∆r gj designates the Gibbs functions for the reac-
tions j (j = 1 or 2). By introducing the respective expressions
of the chemical potential, the following equation is eventu-
ally derived:

1 dg = ln 1 ξ1 dξ1 ξ2 dξ2
+ ln 1 (18)
RT dt K 1 1 – ξ1 – ξ2 dt K 2 1 – ξ1 – ξ2 dt
c d

Figures 8a and 8b display the evolution of the Gibbs func-

tions for reactions 1 and 2 together with the rates of reac-
tions 1 and 2 as a function of time on two time scales (a:
short; b: long). Under kinetic control, Gibbs functions for both
reactions are negative and increase sharply, whereas the cor-
responding rates are positive and drop rapidly. At interme-
diate times, the Gibbs function for reaction 1 is positive,
whereas that for reaction 2 remains negative. At the same
Figure 8. Evolution of Gibbs function for reactions 1 and 2 together
with the rates of reactions 1 and 2 as a function of time on two time
scales (a: short; b: long). Evolution of rates of Gibbs free energy
changes associated with both pathways (1 and 2; lines) and the
whole system (filled circles) as a function of time on two time scales
(c: short; d: long). The following kinetic constants were used: k1 =
3.5 min
1; k2 = 0.32 min-1; k
1 = 6.9×10
2 min
1; k
2 = 1.8×10-4 min
1.

198 Journal of Chemical Education • Vol. 75 No. 2 February 1998 • JChemEd.chem.wisc.edu

 Research: Science & Education

time, the rate of reaction 1 becomes slightly negative formed into

whereas that of reaction 2 is positive and almost opposite. k
1 P1
Indeed at this stage, ξ1 + ξ2 ≈ 1 so that dξ1 =
dξ2. Beyond τ2, R =
k1 + k2
the Gibbs functions and rates for both reactions tend to zero.
Figures 8c and 8d display the evolution of rates of Gibbs free Hence
energy changes associated with both pathways (1 and 2) and d P1 k
1k 2
with the whole system (markers on the figures). It can be – = k obs P1 = k
1 P1 – k 1 R = P1
dt k1 + k2
shown (i) that contributions from both pathways 1 and 2 are
negative and (ii) it is essentially pathway 2 that drives the k
1k 2
evolution process. Expressed in another way, the Gibbs free k obs = (A1)
k1 + k2
energy reservoir associated with pathway 2 is large enough
to counterbalance the unfavorable aspect of reaction 1, which Since kobs = ln 2/120 = 5.8 × 10
3 min
1, k2 is calculated to be 0.32
tends to disfavor the whole reaction process. min
1.1 Equation 5 eventually gives k
2. Indeed,

Acknowledgments
We are indebted to P. Le Guennec for his help in draw-
ing Figure 7a. We also wish to thank E. A. Maatta for his
help to improve the manuscript.
Literature Cited
1. Atkins, P. W. Physical Chemistry, 5th ed.; Oxford University Press:
Oxford, 1994.
2. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, 3rd ed.;
Plenum: New York, 1990.
3. Peckam, G. D.; McNaught, I. J. J. Chem. Educ. 1992, 69, 554–558.
4. Snadden, R. B. J. Chem. Educ. 1985, 62, 653–655.
5. Johnson, C. E.; Eisenberg, R. J. Am. Chem. Soc. 1985, 107, 3148–3160.
6. Benson, S. W. The Foundations of Chemical Kinetics; McGraw-Hill:
New York, 1960.
7. Spencer, J. N. J. Chem. Educ. 1992, 69, 281–284.
Appendix 1
Extraction of Kinetic Constants from Original Data at 25 °C
Data
1. The reactant R [IrBr(CO)(dppe)] is completely con-
verted into the products P1 and P2 in less than 1 min
in a benzene solution at 25 °C.
2. During the first phase of this evolution, [P1]/[P2] > 99%.
3. The reaction of P1(H2) with D2 yields P1(D2) before
isomerization to P2 with a half-time of 10 min at 25 °C
in the benzene solution.
4. In the benzene solution at 25° C, the isomerization re-
action P1 → P2 is typically halfway complete in 2 hours.
We will assume it to obey first-order kinetics (kinetic
constant kobs) as demonstrated for acetone solution.
5. At equilibrium at 25 °C, in the benzene solution,
[P2]∞/[P1]∞ = 35.
Determination of Kinetic Constants
By assuming that the isomerization proceeds according to ki-
netic scheme 1 (eq 1) in the presence of an excess of hydrogen as
suggested by the authors, the kinetic constants can be easily de-
rived. Equation 1 gives k1 + k2 directly. Since the reaction is first
order, and assuming that the half-time is equal to about 0.2 min
(after 5t1/2, [R] ≈ 0),
k1 + k2 > ln 2 /0.2 = 3.5 min
1
Since the selectivity during the first evolution regime is more than
99% (eq 2), k1 >> k2, so that k1 = 3.5 min
1. Equation 3 gives k
1.
Since the reaction is pseudo first order (excess of D2), k
1 = ln 2/10
= 6.9 10
2 min-1. Equation 4 gives k2. As emphasized in the text,
[R] ≈ 0 when t > t1—that is, after the regime of kinetic control. By
applying the principle of the quasi steady state to R during the
second regime of evolution (t1 < t < t2), one has:
dR
=
k 1 + k 2 R + k
1 P1 + k
2 P2 = 0
dt
By considering that k
2 and P2 are simultaneously small during the
first half-time of the second relaxation, this equation is trans-
k 2 / k
2
= 35
k 1 / k
1
and k
2 is calculated to be 1.8 × 10
4 min
1.
Thus, the following expressions were obtained:

2 t

4
2
R = R 0
5.5 × 10 + 0.98e
3.88 t + 1.6 × 10 e
5.9 × 10

2
2 t
P1 = ξ1 R 0 = R 0
2.8 × 10 + 0.90e
3.88 t + 0.88e
5.9 × 10

2
2 t
P2 = ξ2 R 0 = R 0
0.97 – 8.1 × 10 e
3.88 t – 0.89e
5.9 × 10
τ1 = 15 s; τ2 = 171 min; K1 = 51; K2 = 1778.
Note
1. k2 is indeed inferior to k1, and the approximation k1 + k2 ≈ k1 is thus
justified. It should be possible to employ this calculated value of k2 to deter-
mine the k1 value and proceed by iteration until convergence. Here, only an
order of magnitude was desired and the iterative procedure was not applied.
Appendix 2
Evaluation of Standard Activation Enthalpies
of Isomerization Reactions
The only information about the effect of temperature on the
kinetic constant kobs for the isomerization of [IrBr(CO)(dppe)] is
for acetone solution. Since only a rough estimate is sought, we will
assume for the following that the values are the same in benzene.
The reaction of isomerization is described to follow first-order
kinetics with half-lives t1/2 equal to 35 h at 25 °C and 62 min at 55 °C.
By considering eq 14 and that t1/2(T) = ln 2 / kobs(T), it is possible
to calculate the standard activation enthalpy of the isomerization
P1 → P2 reaction if it is assumed to remain constant in the domain
of temperatures under consideration. Hence, ∆r H0≠ (P1 → P2) = 93
kJ mol
1. Considering eq 19, and if k2 is neglected in front of k1, the
application of the Eyring equation provides:
∆rG0≠(P1 → P2) = ∆rG0≠(P1 → R) + ∆rG0≠(R → P2) – ∆rG0≠(R → P1)
= ∆rG0(R → P1) + ∆rG0≠(R → P2) (A2)
with ∆rG0(R → P1) =
RT ln(k1/k
1) =
10 kJ mol
1.
Now, since it is only an order of magnitude that is sought here,
we neglect the entropic term of activation so as to write:
∆rG0≠ ≈ ∆rH0≠
Under this assumption, eq A2 gives:
∆rH0≠(R → P2) ≈ ∆rG0≠(R → P2) = 103 kJ mol
1
If one estimates ∆rG0≠(R → P2) directly from the Eyring relation,
one obtains ∆rG0≠(R → P2) = 86 kJ mol
1. The satisfactory agreement
between the two ∆rG0≠(R → P2) values supports the assumption so
as to estimate all ∆rG0≠ and thus all ∆rH0≠ from the Eyring equa-
tion. Consequently, in view of the values of the kinetic constants
and to simplify the calculations, we considered all the ∆rH0≠ to be
equal to 100 kJ mol
1.

JChemEd.chem.wisc.edu • Vol. 75 No. 2 February 1998 • Journal of Chemical Education 199