Effect of concentration on the rate of chemical reactions

C. A. Ward

Citation: The Journal of Chemical Physics 79, 5605 (1983); doi: 10.1063/1.445681
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 Effect of concentration on the rate of chemical reactions
C. A. Warda)
Laboratoire d'Electrochimie Interfaciale du C.N.R.S., 92195 Meudon Principal Cedex, France
(Received 24 May 1983; accepted 16 August 1983)

A method that has recently been used to examine the rate of molecular transport across a phase
boundary-statistical rate theory- is extended to obtain the expression for the rate of a single step chemical
reaction. The concentration dependence of the newly derived rate expression leads to the prediction of a
higher reaction rate in the period immediately after the reaction has begun than any of the previous theories
and gives a different physical interpretation of the "rate constant". When ions are reacting in solution under
near-equilibrium conditions, the concentration dependence of the newly derived rate expression reduces to the
conventional expression; further under these conditions, the new fate expression leaps to an expression for the
conventional rate constant that is equivalent to the Brtlnsted primary salt effect for the change in the rate
constant with ionic strength. To eltamine the predicted behavior in the initial period, the predictions are
compared with the measurements of ion concentration during electron exchange reactions. When these
experiments were originally conducted, using radioactive labeling techniques, substantial disagreement was
found between the conventional theory and the measurements. To bring them together the concept of "zero-
time exchange" was introduced which amounts to adding a constant to the predictions of the conventional
theory. The physical basis for this concept has remained undefined. When the statistical rate theory
expression is compared with the data from six experiments available in the literature, it is found for five of the
six that there is no measurable disagreement between the data and the theory and only small disagreement for
the other case. From the point of view of statistical rate theory it is unnecessary to introduce the concept of
zero-time exchange.

I. INTRODUCTION If A and B of Eq. (1) represent ions in solution that

Suppose it is known that the following reaction occurs
as a single step reaction:
(1)
and it is proposed to predict the net rate at which the
reaction proceeds. To obtain the concentration depen-
dence of the expression for the forward rate of the
chemical reaction J f , a number of theories have adopted
the concept of the reaction proceeding through an acti-
vated complex and assumed equilibrium to exist be-
tween the activated complexes and the reactants. This
assumption waS introduced by Eyring in 1935 and it
leads to following expression for the forward rate of
the chemical reaction!:
Jf= kfCAC B , (2)
are exchanging charge, the usual approach to obtaining
the expreSSion for the rate has been through the absolute
rate theory (Refs. 5 and 6 give reviews of these theo-
ries). Thus all of these approaches lead to an expres-
sion for the concentration dependence of the reaction
rate as given in Eq. (2), but with different approaches
for calculating the rate constant k f • 5,6
A related approach is the reaction-elementary-act
theory aSSOCiated primarily with Dogonadze and Le-
vich. 7,8 Although the approach is quantum mechanical
in nature, they abandon the formalism of quantum me-
chanics and define the rate to be of the form [see Ref.
8, Eq. (2.1))
Jf=CAC B i""
TO
W(R)P(R)dR , (3)

where C; is the concentration of species i and k f is the
rate constant in the forward direction.
The assumption of equilibrium between the activated
complexes and the reactants has been questioned be-
fore, 2,3 but the approach to examining this assumption
has been through the Boltzmann equation and this equa-
tion contains the assumption of molecular chaos 4 (which
amounts to assuming that there is no correlation between
reacting molecular pairs). Such an assumption is also
questionable when a reaction is occurring at a high rate.
If one considers the level of approximation at which k f
is time independent and assumes that the distribution
over the internal states of the reactant molecules is the
Maxwellian distribution, then the approach through the
Boltzmann equation leads to Eq. (2) as well. 2,3
aJpermanent address: Department of Mechanical Engineering,
University of Toronto, Toronto M5S lA4, Canada.
where P(R) is the probability that ions approach to a
distance R and W(R) is the probability (per unit time)
that an electron performs the tranSition between A and
B when they are separated by the distance R. Note
that by proceeding in this fashion they have hypothesized
the concentration dependence of the rate (rather than
deriv ing it from quantum mechanics) and the hypothes ized
dependence is the same as that of absolute rate theory.
Thus all of the previous theories for a chemical reaction
of the type shown in Eq. (1) would predict the same Con-
centration dependence for the reaction rate as shown in
Eq. (1), although the basiS for this dependence would
vary.
In the 1950's it became possible to examine experi-
mentally the dependence of the rate expression on the
concentration of the constituents for a single step reac-
tion using radioactively labeled components. 5 This
method was used to study electron exchange between

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 5606 C. A. Ward: Effect of concentration on chemical reactions
ions of the same basic chemical component and it was
possible to follow a reaction sequentially from shortly
after the reactants were brought together until the sys-
tem was near equilibrium.
To predict the concentration as function of time, it
is necessary to take into account the reverse reaction:
(4)
The potential between such ions is said to be symmetric 9
so that kT and kl are taken to be equal. The concentra-
tion of the radioactively labeled product may then be
predicted as a function of time from Eqs. (2) and (4).5
When this predicted concentration was compared with
the measurements strong disagreement was found during
the initial period of the reaction (e. g., see Refs. 10-12).
The experimental values being considerably larger than
those predicted. However by this time the rate expres-
sion in Eq. (2) occupied such a hallowed pOSition in
chemical kinetics that the experimentalists chose to de-
cide that there was something wrong with the experi-
mental technique, rather than to decide that there was
something wrong with the rate expression given in Eq.
(2); they therefore chose to add a constant to the pre-
dicted concentration obtained from Eqs. (2) and (4).
This constant was referred to as the "zero-time ex-
change". The idea was that this amount of product was
being produced in some unspecified way in the experi-
ment. By adding this constant, they could bring their
experimental values into agreement with the theoretical
expression obtained from Eqs. (2) and (4). This amounts
to ignoring the data in the initial period and determining
the rate constant approximately from the data in the
near-equilibrium period; this procedure is discussed
further below.
We would wish to emphasize the similarity between
this experimental situation and that which was noted
recently for gas adsorption on a solid surface. Many
experimental studies had indicated a much more rapid
rate of adsorption immediately after exposure of the
gas to solid than was predicted on the basis of absolute
rate theory. 13 Adsorption during this early period was
sometimes referred to as nonactivated. 14-16
When a recently developed theoretical procedure for
predicting the rate of molecular transport across the
interface between two phases 17 was applied to predict
the rates of nondissociative13 and dissociative adsorp-
tion,18 it was found to give predictions consistent with
the measurements, even in the period immediately after
the exposure of the solid surface to gas. The same the-
ory was also applied to predict the rate of gas absorp-
tion by a liquid. 19 For this latter case, it is possible
to make a complete prediction of the rate and when the
predictions were compared with a set of measurements
they were found to be in close agreement. 19
Using this same theoretical procedure-called sta-
tistical rate theory16-we propose t'o develop the ex-
pression for the rate at which a chemical reaction of
the type indicated in Eq. (1) proceeds. We adopt the
formalism of quantum mechanics and allow it to lead
to concentration dependence of the rate expression. The
J. Chem. Phys., Vol. 79, No. 11, 1 December 1983
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concentration dependence of the derived expression is
different from that of any of the previous theories, and
the "rate constant" has a different physical interpreta-
tion. However when the derived expression is applied
to consider the rate of reaction between ions in weak
solution under near-equilibrium conditions, the concen-
tration dependence of the rate expression reduces to
the conventional expreSSion [Le., Eq. (2)], and when
it is assumed that under equilibrium conditions the ions
fluctuate between associated ion pairs and free ions,
the Brpnsted primary kinetic salt effect20 is predicted
for the change in the rate constant with ionic strength.
As a result of the derived concentration dependence
of the new reaction rate expreSSion, it is predicted that
the rate will be initially higher than that predicted by
the previous theories. To examine this prediction we
compare the concentration dependence predicted from
the new reaction rate with the available measurements
for electron exchange between ions in solution. Close
agreement is found even in the initial period, and in
particular it is found that there is no need to introduce
the (still unexplained) concept of zero-time exchange. 21
II. TRANSITION PROBABILITY AND THE RATE OF
CHEMICAL REACTIONS
Consider an isolated system that is spatially homo-
geneous and consists of r chemical components. Sup-
pose that four of the components react according to the
scheme of Eq. (1). Let the number of molecules of com-
ponent s be denoted N s ; then the number of molecules of
each component at the instant t1 may be denoted as A1
where
Al : N~, N~, N~, ... ,N; . (5)
We propose first to construct the expreSSion for the
probability of the system making a change in molecular
distribution corresponding to it undergoing a single step
in the reaction defined in Eq. (1). We shall adopt the
quantum mechanical formalism. In determining this
rate from quantum mechanics, it should be noted that
it is impossible to specify the path by which the system
goes from one molecular distribution to another. One
is concerned only with the molecular distribution before
the change and after.
Suppose the molecules of the system are constrained
to be in a particular distribution Al and let the Hamil-
tonian operator for the system in this constrained con-
dition be denoted as li o• When the molecules of the sys-
tem are free to react (1. e., subjected only to their
physical potentials), the Hamiltonian operator is de-
noted as iI. We may then define a potential operator V
as follows:
(6)
and the Schrodinger equation may then be written
(7)
where if! is the wave function for the system; Ii is Planck's
constant divided by 21T and i is the unit imaginary num-
ber. Physically, when both iIo and V are acting, the
 C. A. Ward: Effect of concentration on chemical reactions
components can react at their normal rate. We shall
assume that I V1/J I is small compared to Iilol/ll; hence
one can apply perturbation theory to construct the ex-
pression for the wave function. 22 The eigenfunctions
U::(g) and eigenvalues E~ of flo are obtained from
If u~(g) = E~ u~(g) , (8)
where g are the generalized coordinates for the system.
In principle the eigenfunctions for the operators flO could
be constructed corresponding to all possible molecular
distributions of the system and the wave function ex-
pressed as
I/I(g, t) =L bv(t) u~ exp( - iE~ tlli) . (9)
v
Among the eigenfunctions are those corresponding to
the molecular distribution A/
(10)
These eigenfunctions will be denoted u~(g) and their total
number by n(A i ). After one forward step of the reaction
the distribution will be
Ak : N~ -1, N~ -1, Nb + 1, Nt + 1, ... , N~ • (11)
The eigenfunctions corresponding to this distribution
will be denoted u~(g) and we suppose there to be n(Ak)
such functions. Let
t=tk - tj . (12)
To describe the fact that the system is initially in mo-
lecular distribution AJ we adopt the ensemble description
so that the initial value of the coefficient b,,(ti ) satisfy
the relation:
(13)
where the double bar refers to the ensemble average of
a quantity. One may now follow the standard procedure
of first order perturbation analysis to construct the ex-
pression for the probability of a transition from Ai to
Ak at any instant in time, r(Aj' Ak)22'23:
r(Ai' Ak) =K(Ai' Ak ) n(Ak)/n(A i ) , (14)
where
(15)
and it has been assumed that the energy of the system is
constant to within its uncertainty, ~E; wi(E) is the mi-
croscopic state density evaluated at the mean energy of
the system, and I Vik I is the average of the absolute
values of the transition matrix elements of the operator
V for the transition from the microscopic states of the
molecular distribution Ai to states of molecular distri-
bution Ak •
~ter neglecting the difference between wJ(E) and
wk(E) and taking advantage of the Hermitian property of
the transition matrix elements one finds
(16)
We now follow the statistical rate theory procedure17
to construct the expression for the unidirectional rate
of transitions from AJ to Ak, i. e., J,(A j , Ak), and find
J,(AJ,Ak)=K(AJ,Ak)exp[S(Ak)-S(ANk] , (17)
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5607
where we have made use of the Boltzmann definition of
entropy. 11
At that same instant that there is a probability for a
transition from molecular distribution Ai to Ak, there
is a probability for a transition from Ai to Ai where Ai
is the molecular distribution resulting from the reac-
tion taking place one complete step in the reverse di-
rection:
AI : N~ + 1, N~ + 1, Nb -1, Nb -1, ... , N: . (18)
Following the same procedure as that outlined above,
one finds for this rate, i. e., J~, that
(19)
where K{A j , Ai) is
K(Aj' AI) = (21T/1l) w/E) VJi I 12 (20)
Finally, we take as the expression for the net rate at
which the chemical reaction proceeds in the forward di-
rection J, the difference in the two unidirectional rates
given in Eqs. (17) and (19):
J =K(A , Ak ) exp [S(A k) ~ S(A j ) ]
j
_ &(A. A ) [S(A I) - S(A 1) ]
I exp k (21)
J'
In the following section this expreSSion for the net rate
at which the chemical reaction proceeds will be put in
a more usable form by making use of thermodynamic
relations to evaluate the difference in the entropies.
III. RATE OF A CHEMICAL REACTION EXPRESSED
IN TERMS OF CHEMICAL POTENTIALS AND THE
EQUILIBRIUM EXCHANGE RATE
The system will be assumed to be close enough to
equilibrium so that the thermodynamic properties are
well defined and the entropy may be expressed:
~
S =(liT) U + (piT) V - Ls (J1. slT) Ns , (22)
where T is the temperature, P the pressure, and J1. s
is the chemical potential of component s. We shall as-
sume that none of the intensive thermodynamic proper-
ties are changed as a result of the system undergoing
one reaction step; thus for the isolated system we con-
sider one finds:
S(Ak) - S(A i ) =(liT) [J1. A(Aj) + J1.B(Aj) - J1.C<~) - J1.D(Aj)l , (23)
S(AI) - S(Ai) =(liT) [- J1.A(Ai) - J1.B(A i )+ J1.c(A i ) + J1.D(A i )] ,
(24)
and the instantaneous net rate of the reaction in the
positive direction when the system is in molecular dis-
tribution Ai can be written from Eq. (21) as
J i =K(Aj, Ak)~i - K(A i , AI)~? , (25)
where ~j is defined by
~i =exp{[J1. A(A J) + J1.B(A J) - J1.C(A i ) - J1.D(A J) l/kT}. (26)
It remains to investigate K(AJ' Ak), K(AJ' AI), but note
that ~J only depends on the instantaneous molecular dis-
tribution AJ •
 5608 C. A. Ward: Effect of concentration on chemical reactions
First, we consider the expression for the rate when
the system has reached the stable equilibrium state.
A necessary condition for equilibrium of a system in
which the reaction of Eq. (1) occurs is that
where Ae denotes the equilibrium molecular distribution:
Ae: ~,N"s,N2,~, ... ,N;. ;
N".is the equilibrium value for the number of molecules
of component s. Let AI' Ad denote the molecular distri-
butions on either side of equilibrium:
Af : N;. - 1, ~ - 1, m+ 1, ~ + 1, ... , N'. ,
Ad: N;.+I,~+I,m-l,~-l, ... ,N'..
According to Eq. (27), .:le is unity and since the equi-
librium state is supposed stable, the net rate of decay
from this state must vanish so that from Eq. (25) one
finds
K(Ae, Ad) =K(Ae, AI) • (31)
For later use it is important to have a physical under-
standing of K(Ae, Ad), K(A e, Af). We find they are the
equilibrium exchange rates for the reaction. This may
be seen by noting that according to Eqs. (17), (19), (23),
(24), and (27) the unidirectional rates for the reaction
J(A., Ad) and J(Ae, Af) reduce to K(Ae, Ad), K(Ae, AI) respec-
tively in equilibrium, and according to Eq. (31) these
unidirectional rates are equal. Thus they are the equi-
librium exchange rate for the reaction and will be de-
noted Kx. In Ref. 17 it is pointed out that Kx may also
be examined at the microscopic level. It is found to be
the average rate at which the system makes a transition
between microscopic states of neighboring molecular
distributions.
From Eq. (16) we may rewrite Eq. (31) as
K(Ae, Aa) =K(A e , Af) =Kx •
Then following Ref. 17 we shall introduce the hypothesis
that an equation of the type shown in Eq. (32) is valid
for transitions between any two distributions; thus
Kx:= K(Ad' Ae):= K("Ae, Af)
(33)
At the microscopic. level, Eq. (33) amounts to assuming
that the average rate at which the system makes transi-
tions between microscopic states of neighboring molecu-
lar distributions is the same for all distributions; thus
this rate is independent of the number of states corre-
sponding to a distribution. 17 At the macroscopic level
this rate must, according to Eqs. (31) and (32), be
equal to the equilibrium exchange rate for the reaction.
One of the immediate consequences of Eq. (33) is that
the expression for the net rate at which the chemical
reaction proceeds may be written for any distribution as
(34)
and since J j and .:lJ only depend on the instantaneous
molecular distribution we have dropped the subscript j.
The important considerations of the equilibrium ex-
change rate Kx remain to be made. For the macroscopic
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constraints we consider, there is one stable equilibrium
state for the system; thus Kx is a constant. However,
to determine its value will require speCification of the
mechanism by which the exchange takes place under
equilibrium conditions; i. e., such quantities as the num-
(27)
ber of encounters between the reactants and the prob-
ability of a reaction occurring in an encounter. However,
since we are only concerned with equilibrium conditions,
(28)
a number of simplifications are applicable.
From Eqs. (17), (19), (23), (24), and (26), one can
see that the rate at which the reaction takes place in the
forward direction is Kx.:l and in the reverse direction is
(29) Kx.:l- 1 • The non equilibrium effects are contained in the
term.:l. Note that the non equilibrium effects do not by
(30)
themselves create a net chemical reaction. If under
equilibrium conditions the exchange rate for the reaction
is zero, then under nonequilibrium conditions it is zero
as well.
Equation (34) gives the basic expression for the pre-
dicted rate of the chemical reaction. Below we apply
it to the special case of electron exchange between ions
in solution with the aim of assessing its validity.
IV. REACTIONS IN SOLUTION
Suppose the reactants are ions in solution; the chemi-
cal potentials may then be written:
IL" := IL ~ (T, P) + k T In a", , (35)
where 0' can be equal to A, B, C, or D; a", is the activity
of component 0' and IL~ is the reference chemical poten-
tial of that component in the solution.
For a system in which a reaction of the type shown in
Eq. (1) takes place, the condition for equilibrium is
given in Eq. (27); thus for equilibrium to exist
K - aCe aD. (36)
(32)
e-aAeaBe '
where the subscript e on a property indicates an equi-
librium value; Ke is the equilibrium constant and is
given by
Ke = exp[(IL~ + IL~ - IL~ -1L~)/kTl . (37)
Then .:l from Eq. (26) may be written
(38)
Thus the unidirectional rate at which the reaction pro-
ceeds to the right J/(A j , Ai) is from Eqs. (17), (23), (26),
and (33) given by
(39)
One finds Similarly for the unidirectional rate at which
the reaction of Eq. (1) proceeds to the left, i. e. ,
Jr(A j , AI) that
Jr(A j , AI) :=KxaDaC/KeaAaB , (40)
and for the net rate of the reaction J from Eq. (34) that
J=Kx [(KeaAaB/aDaC> - (aDaC/KeaAaB)] • (41)
The expression in Eq. (41) is the expression for the
rate obtained from statistical rate theory when the re-
 C. A. Ward: Effect of concentration on chemical reactions
action of Eq. (1) takes place in the solution. Below we
shall use it to predict the concentration as a function of
time for a particular set of reactions, but first we com-
pare a limit of this relation with the conventional expres-
sion.
v. RELATION BETWEEN THE STATISTICAL RATE
THEORY EXPRESSION FOR THE CHEMICAL
REACTIONIRATE ANDITHATIOF PREVIOUS THEORIES
From Eqs. (2) and (4) one finds that the expression
for the net rate of the reaction, J', according to all
previous theories is of the form
The previous theories would disagree as to the approach
to be used for the calculation of ki' k .. but they would
::tgree that the concentration dependence of the reaction
rate is as shown in Eq. (42).5
Because of the assumptions in the absolute rate theory
approach one might expect it to be valid when the sys-
tem is close to equilibrium, and in this limit there is
considerable empirical support for that approach. Thus
we shall examine the expression for the chemical reac-
tion rate obtained from statistical rate theory in the near
equilibrium limit to see if it reduces to the conventional
expression. The case we shall consider is that of re-
actions in solution. For this particular case, the Brpn-
sted primary salt effect has been established empiri-
call14.25 and it forms a part of the basis for the idea of
an activated complex in the conventional approaches to
chemical reaction rates. It is of interest to see in what
way the Brpnsted primary salt effect is obtained from
the approach developed above.
It should be emphasized that in obtaining the expres-
sion for the reaction rate in Eq. (34) from the statisti-
cal rate theory approach no concept has been intrOduced
of the reaction path being through an activated complex.
Indeed, no concept of the reaction path has been intro-
duced. This results from the fact that the basis for the
statistical rate theory approach is quantum mechanical
and the path by which a change takes place is not intro-
duced in quantum mechanics.
As the definition of the near-equilibrium condition,
we suppose that the parameter E is small compared to
unity where E is defined by
and we shall suppose that the displacement from equi-
librium by both reactants and products is symmetrical
so that the following sum has the same value in the non-
equilibrium states as it does in equilibrium, i. e. ,
-1 (a. a.. + ---"'--"'-
----"'--"- an aro) = 1
2 a"'eaBe aDeaCe .
Equations (43) and (44) may then be solved simultaneous-
ly to give
a",aB ~ _ 1+E
a"'e aBe aD ac - 1- E
and after making use of the expression for the equilibri-
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5609
um constant given in Eq. (36) and using Eq. (45) in Eq.
(41), we may write the chemical reaction rate expres-
sion as
(46)
Since E is small compared to unity, one may expand
Eq. (46) and write
(47)
and retaining terms to second power in E one finds that
the near equilibrium limit of the rate J. is
J. =Kx(4E) (48)
(42) and thus
J =2K
"
(~-~)
x aAeaBe
aDeaCe
(49)
Finally on examining Eq. (49) one may identify the uni-
direction rates. Thus the near-equilibrium unidirec-
tional rate in the positive direction is given by J'n:
(50)
where we have introduced the activity coefficients Ys
that are defined from the relation
(51)
After comparing Eq. (49) with Eq. (3) one may identify
the expression for the conventional rate constant k"
i. e.,
(52)
and with this identification the near-equilibrium limit
of the statistical rate theory expression is seen to re-
duce to the conventional expression.
Note that in Eq. (46) the ratio 2Kx/aAeaBe is a ratio
of equilibrium properties and is strictly constant. For
example, suppose one considers a reaction of the type
indicated in Eq. (1) in which ions 'lZI, ~2 are reacting
in solution where ZI and Zz are the charges on the ions.
Under equilibrium conditions, we suppose that the sys-
tem fluctuates between associated ion pairs and free
ions so that Eq. (1) may be expanded to write:
(53)
where <5 denotes the associated ion pair and Zl +Z2 is its
charge. Since we are considering equilibrium condi-
tions we may write without assumption:
(54)
(43)
where K~ is the equilibrium constant between the ions
a·l , ~2 and the complex (0)·1··2. Then equation (52)
may be written
(55)
where Y~e is the activity coefficient for the ion com-
(44) plexes and c 6e is their concentration.
To understand this relation physically we consider it
in the dilute limit in which the Debye-Hiickel expres-
sion for the activity coefficients is valid. If we suppose
the ions are in aqueous solution at 25 ee, then the
(45)
Debye-Hiickel relation may be written 26
(56)
 5610 C. A Ward: Effect of concentration on chemical reactions

where I is the ionic strength; for the associated com-
plex:
After taking the logarithm of Eq. (55), inserting Eq.
(57), and simplifying, one finds the result may be
written in the form:
log10kf=B+1.018z1zzI1/Z,
where B is defined by
B =10g10 (~K,,/ c 6e ) • (59)
Note that B is constant for a given system. The rela-
tion given in Eq. (58) is equivalent to the well-known
Brpnsted primary salt effect showing the effect of the
ionic strength on the conventional rate constant. 20 It
has substantial experimental support. Z4,25 Note that in
obtaining this relation no concept is introduced of equi-
librium between an "activated complex" and the reac-
tants while the reaction is taking place.
VI. ELECTRON EXCHANGE REACTIONS BETWEEN
IONS IN SOLUTION
It has been seen above that the statistical rate theory
expression for the rate of a chemical reaction reduces
to the conventional rate expression in the near-equi-
librium limit. However, comparing the statistical rate
theory expression (41) with the conventional expres-
sion (4) shows that they predict very different re-
sults when the amount of products is small, i. e., in
the early period of the reaction. In this section we pro-
pose to examine this difference in the predictions by
comparing the two rate equations with the previously
reported experimental results.
We consider electron exchange between ions of the
same basic component in solution and suppose that the
reaction is followed by radioactively labeling one of
(57)
them; thus as a special case of Eq. (1) we may write
*A+A+=*N+A, (60)
where the superscript • denotes a radioactively labeled
component; A is an ion and A+ is an ion of the same ele-
(58) ment in one higher state of ionization. We suppose that
the activity coefficients for the labeled and unlabeled
ions are equal (which would be exactly true within the
Debye-Huckel approximation); then according to statis-
tical rate theory, the net rate may be written from Eq.
(41):
J =Kx (C A+ C.AKe/CAC. A+ - C AC.A+/K.,CA+C.A). (61)
After introducing the reaction variable Y that is equal to
the concentration of the labeled product, one finds that
Eq. (61) leads to
(dy/dt) =Kx {(a - y) ({3- y)/l- [l/(a - y)({3- y)]} ,
(62)
where a, (3 are the initial concentrations of components
• A and A+, respectively, and the equilibrium constant
has been taken as unity because of the similarity of the
labeled and unlabeled ions. From Eq. (36) one then
finds that at equilibrium:
Ye =('l!{3/a +(3) . (63)
Equation (62) may be integrated exactly. One finds
from separation of variables and expansion in partial
fractions that if y vanishes initially and if the initial
ratio of the concentrations satisfies the condition
0.1715<{3/a<5.82 , (64)
then

Kxt = [a{3( a Z+ (3z)/ 4( a + (3)3] (Y/Ye) - [a Z{32 /4( a + (3)3](y/ Ye)Z - [aZf /2( a + (3)3] In(1 - Y/ Y.) + [(a + (3)/ 16] In[2a{3(1/ a + (3)2
X (y/y.)z _ (Y/ Ye) + 1] + (a - (3)2/8'; 6a {3 - (a Z+ (32) [tan -1({[ 4a{3y/ Y.( a + (3)] - (a + (3)}/v' 6a13 - (a Z + (3Z»
- tan- 1 [- (a + (3)J" 6a{3 - (a 2 + (32)]] . (65)
When (3/ a does not satisfy the condition of relation (64) one finds
~t = ya{3(a z + f)/4Ye( a + (3)3 - aZ{3V/4y~(a + (3)3 - [a zr:J2j2(a + (3)3] In(1 - y/Ye) + (a z - {3zW640(a + (3)z

+ [(az _ fW640(a + (3)Z] In { [4( a{3/ Q! + (3)(y/ Ye) - (0' + (3 + 40)] (40 - 0' - (3) } + (0' + (3/16) In{2[a{3/(O' + (3)Z]
[4(O'{3/a +(3) (Y/Ye) - (0' +(3- 40)] (-41i - 0' - (3).
(66)

i. e., when
{3/O'<0.1715 or {3/O'> 5.82 .
If one adopts the conventional rate expression (42),
then it may be simply integrated as well. One finds,
since k f and kr are said to be equa1 9:
kt =(0' + (3)"11n(1 - y'/Ye)"1 ,
where Y' is the concentration of the labeled product and
it has also been required in this case that y' is initially
zero.
To compare the available measurements with either
the predictions from statistical rate theory or from the
conventional rate expression, it is necessary to choose
(67) a value of either Kx or k. We shall choose values of
each of these such as to minimize the square of the total
error in each of the respective cases.
Suppose that a set of data is available so that a set of
(68) n values of Y/Ye are given at times tl> then we take as
the definition of the square of the error:
(69)
where t~ is the predicted time at which the concentra-

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 C. A. Ward: Effect of concentration on chemical reactions 5611

~----------~------------,

tion ratio has the value Y/Ye'

1.0
First consider the predictions from statistical rate ----
theory. Equations (65) or (66) may be viewed as being 0.9
of the form ~0.8
(70) ~07 /
/'
/
where F(y/ Ye) is the right-hand side of either Eq. (65) 206
o . /
a:: /
or (66), then Eq. (68) may be written as c: 0.5 /
o /
/
(71)
'E 0.4 /
-=~ 0.3 I
/
u I
After requiring that the first derivative of E2 with re- § 0.2 /
spect to K" vanishes, one finds the value of K" which u
0.1 /
I
minimizes the error to be given by

Xx= t F(YJYe)/t. tj • (72)

2 3 4

FIG. 2. Same comparison as that of Fig. 1 and same condi-

5 6 7
Time (Min)
8 9 10 11 12 13 14

The value of Xx determined in this way will be used be- tions except the hydrogen ion concentration was 0.4 M. See
low to compare the predicted concentration with the Table I.
measurements.
For the conventional rate expression one may also A. Comparison of predicted concentration as a function
use this procedure to obtain a value of k which mini- of time with available experimental data
mizes the error. If Eq. (68) is viewed as being of the
form: Previous studies of electron exchange between ions in
solution provide some data on the concentration as a
kf=!(y'/Ye) , (73) function of time for a reaction of the type shown in Eq.
then the value of k which minimizes the total error (60). The usual procedure is to label an ion radioac-
squared is tively, mix the components together, and measure the
rate of charge transfer by measuring the appearance of
(74) a product ion, using separation techniques. 27.28
Although these reactions have been extensively stud-
In comparing the predictions from the statistical rate ied,5.6 very little of the data has been reported in suffi-
theory approach and from the conventional rate theory cient detail to allow it to be examined from a new theo-
expression we shall choose Xx and k on the same basis, retical point of view. Rather, the usual procedure is
i. e., from Eq. (72) and (74), respectively. to give only the rate constant inferred from absolute
rate theory. The principal exception to this is Wahl
and his co-workers who usually report the concentration
as a function of time for at least one experiment. 10-12
1.0 This will allow us to compare our predictions with their
experiments for three different types of ions. It was
0.9
also Wahl and his co_workers10- 12 ,29 who most clearly
~0.8 pointed out the difficulty of the zero-time eXChange, al-
~0.7 though the concept was later briefly discussed by Rey-
o nolds and Lumry in their reviewS and by Lipkowski et
ii 0.6
a: . al. 21
c 0.5,
~ 0.4
1 A second method that has been used to study these re-
actions is nuclear magnetic resonance. 30,31 In this
-=~ 0.3
u
method there is no change in the concentration as a func-
§ 0.2 / tion of time; however as will be discussed below these
u / methods measure K" directly.
0.1 I

2 3 4 5 6 7 8 9 10 11 12 13 14 1. Electron exchange between vanadium ions in solution

Time (Min)
FIG. 1. Comparison of the measured concentration (solid dots
with 10% error bars) for the V2+, V3+ electron exchange reac-
tion with the calculations from statistical rate theory (solid
line) and with the conventional theoretical expression (dashed
line). Both theories are required to be initially zero. The
data is that of Ref. 12. The medium was an aqueous solution
of HCIO, with 1.00 M If" and the ionic strength adjusted to 2.00
by addition NaClO,. The initial conditions and the inferred
equilibrium exchange rate are given in Table I.
Krishnamurty and Wahl12 have reported the concentra-
tion as a function of time for the following reaction:
(75)
for three different hydrogen ion concentrations. The
reaction took place in 1. 00 f HCIO, with ionic strength
of 2. 00 and the hydrogen ion concentration was varied
at constant ionic strength by addition of NaCIO.. Their
data is shown in Figs. 1-3. Since the initial concentra-

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 5612 C. A. Ward: Effect of concentration on chemical reactions

1-------- ~------------~----

period. Note that the measurements are above the pre-

1.0 ----------- dictions in each case; thus the discrepancy could not be
0.9 explained by incomplete mixing or difficulties with flow.
These difficulties would tend to decrease the rate and
:.: 0.8
thus would give measurements less than the theory.
~0.7 The discrepancy is too large to be explained as inaccu-
,go 06
. racies in measurements in time. One possible explana-
a: tion is an ineffective quenching procedure, but this ex-
c: 0.5
o planation has not been established by further experimen-
'E 0.4 tation. 12
t 0.3
u When first introduced the zero-time exchange was
§ 0.2 a small percentage of the total. 29 However for some
u
0.1 systems studied later that had higher rates of exchange,
the percentage was significantly increased. For exam-
2 3 4 5 6 7 8 9 10 11 12 13 14 ple, for the case shown in Fig. 2, the zero-time ex-
Time (Min) change was greater than 40% of the total. Hudis and
FIG. 3. Same comparison as that of Fig. 1 and same condi- Wahl 29 point out that the apparent zero-time exchange
tions except the hydrogen ion concentration was 0.19 M. See is reproducible for a given set of experimental condi-
Table 1. tions.
If one accepts the validity of the statistical rate theory
tions are equal in each case, Eq. (65) gives the pre- approach for the moment, then it is clear that there is
dicted concentrations as a function of time according to no need to introduce the zero-time exchange concept.
As may be seen in Figs. 1-3, the results obtained from
statistical rate theory, and the solid line in each of these
statistical rate theory are in agreement with the data.
figures shows the results calculated from Eq. (65) where
Also one can understand why the previous theories gave
the value of Kx has been chosen so as to minimize the
consistent results for the rate constant k: by introducing
total error. The values of ~ are given in Table I. The
the zero-time exchange, the previous theories are in
error in this type of experiment has been estimated as
essence being fitted to the data only at later times. As
10%28 and 13%.31 We have shown error bars of 10%,
has been pointed out above, the previous expressions for
based on these estimates. No repeated experiments
the rate of the chemical reaction are in agreement with
were reported.
statistical rate theory in this limit, and thus should
Note that in each case there is close agreement be- lead to consistent results for k.
tween the predictions from statistical rate theory and
The value of k reported by Krishnamurty and Wahl for
the measurements, even in the period initially after the
each experiment is listed in Table I. These values were
reactants were brought into contact.
inferred by assuming a zero-time exchange of 30%, 30%,
This agreement between statistical rate theory and the and 43% of the equilibrium exchange. If one does not
measurements is in contrast to what one finds if the re- assume a zero-time exchange, but requires that the
sults from the conventional rate theories are compared previous theories have zero amount of product at zero
with the results. This comparison can be seen by com- time, then the value of rate constant inferred from the
paring the dashed line in Figs. 1-3 with the experimen- data is changed. The value of the rate constant inferred
tal results. In each case, there is strong disagreement on the basis of minimum total error and no product ini-
between these theories and the experiment in the initial tially present is listed in Table I as k o. Note that the

TABLE 1. Comparison of rate constants.

(A) Electron exchange between y2+ and y3+ at 25°C; see Figs. I, 2, and 3
W/M a/f {3/f K:r Xl04/f min-l k o/(fminr1 k/(fminr1
1.00 0.086 0.086 3.87 1.273 0.79
0.40 0.086 0.086 6.5 1.415 1, 06
0.19 0.086 0.086 11.44 2.7 2.01

(B) Electron exchange between Mn04 and MnO~-; see Fig. 4

k XlO-3/(Msrl

0.1 0.4 0.96 3.6 1.48 1. 38

(C) Electron exchange between Ag+ and Ai+; see Figs. 5 and 6

0.2 10.61 1. 793 1.627 263

11. 4 3.366 4.14 0.1462 ? 648

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 C. A. Ward: Effect of concentration on chemical reactions
value of ko is 60%, 35%, and 30% larger than the value
of k for the three cases shown in this Table.
2. Electron exchange between manganate-permanganate
The kinetics of electron exchange between manganate
and permanganate have been studied both by radioactive
labeling10 and nuclear magnetic resonance. 30,31 In the
case of labeling, the reaction is
*Mn~- + MnO;;: *MnO; + Mn~-
For the only case reported by Sheppard and Wahl the
reaction took place in a weak aqueous solution with sev-
eral ions present. The data obtained for this case and
the conditions are given in Fig. 4, along with the cal-
culations from statistical rate theory [Eq. (65)] and the
value of ~ is given in Table I. The statistical rate
theory approach leads to an overprediction of the data
points during the first 3 s. Since this is the only ex-
periment reported, it is not possible to know whether
this is significant because explanations are easily
imagined, such as a lack of complete mixing during this
early period.
The conventional theory again is significantly below
the data and there is no explanation available other than
the zero-time exchange.
When the reaction is studied with nuclear magnetic
resonance, there is no change in concentration, i. e.,
the reaction is
Mn~- + MnO;;: MnO; + Mn~-
hence the expreSSion for the unidirectional rates as ob-
tained from statistical rate theory, L e., Eqs. (44) and
(45) reduce to the equilibrium exchange rate:
Several values ~ have been measured in Refs. 29 and
30, but there is not sufficient data reported from the
radioactive labeling technique for us to make a com-
. -_ ... __ ._----------------,
1.0
0.9
~0.8
~0.7
~ 0.6
~ 0.5
.2
2 0.4
~ 0.3
§ 0.2
u
0.1
1 2 3 4 5 6 7 8 9 10 11 12 13 14 1·5 16 17 18 19
Time (sec)
FIG. 4. Comparison of the measured concentration (solid dots
with 10% error bars) for the MnOl-, MnO, electron exchange
reaction with the calculation from statistical rate theory (solid
line) and with the conventional theoretical expression (dashed
line). Both theories are required to be initially zero. The
data is that of Ref. 10. The medium was an aqueous solution:
0.16 f NaOH, 0.08 f Na2S0h 4x 10'" f KRe04' The initial con-
ditions and the inferred equilibrium exchange rate are given in
Table I.
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5613
1.0
0.9
~0.8
;:'0.7
. (76)
10
0.2 0.3 of. 0.5 O.s 0:7 0.8 0.9
Time Isec)
FIG. 5. Comparison of the measured concentration as a func-
tion of time for the Ai+, Ag+ electron exchange reaction with
the calculation from statistical rate theory (solid line) and with
the conventional theoretical expression (dashed line). Both
theories are for the mechanism of Eq. (83) and both are re-
quired to be initially zero. The data is from Ref. 11. The
medium was 5.87 f HCI0 4 , at 0.2 ·C. The initial conditions
and inferred value of the equilibrium exchange rate are given
in Table I.
parison of the results obtained for Kx from the two dif-
ferent methods.
3. Electron exchange between silver ions in solution
Although more difficult chemically, one of the fastest
exchange reactions studied with the radioactive labeling
technique is
, (77)
(79)
ll
Gordon and Wahl examined this reaction in 5.87 f
HCI04 and have reported two experiments in which con-
centration as a function of time was measured. This
(78) reaction is of particular interest for two reasons: first,
because its kinetics are very rapid and thus one would
expect it to be a challenge to the conventional rate the-
ories if they are only valid in the equilibrium limit, as
has been claimed above. Second, Gordon and Wahll l
found it necessary to abandon the mechanism of the re-
action being first order in each constituent, i. e., Eq .
(1), and adopted a mechanism corresponding to Ag2+
---- , disproportionating, L e.,
2Ag2+;: Ag3+ + Ag+ (80)
and took the rate expression to be
rate =k( Ci'"g)2 •
(81)
Their main reason for propOSing this mechanism was
because the usual expression for the rate as being first
order in Ag+ and Ag2+, Le., Eq. (2), did not lead to an
adequate fit of the data. However, no measurement of
the presence of Ag3+ was reported and it is a necessary
constituent of the mechanism in Eq. (80).
Gordon and Wahll l report measurements of concen-
tration as a function of time for only two of their many
experiments. Their data for these two experiments are
shown in Figs. 5 and 6. For the values of ~ given in
Table I, the predictions from statistical rate theory ap-
proach are also shown in these Figs. (solid line). The
calculations in this case are from Eq. (65) because the
J. Chern. Phys., Vol. 79, No. 1" 1 December 1983
 5614 C. A. Ward: Effect of concentration on chemical reactions
1.0
0,9
~O.8
:;0.7
,g 0.6
Ii
!5 0.5
'6 0.4
i 0.3
15 0.2
u
0.1
0.2 D.3 0.4 0.5 O.S 0.7
Time Isec)
FIG. 6. The same comparisons as in Fig. 5 and under the
same conditions except the temperature was 11. 4 ·C and the
initial conditions are as given in Table I.
initial concentrations do not satisfy Eq. (64). Note that
no disagreement is observed between the calculations
from statistical rate theory and the data of Gordon and
Wahl.
By contrast, the calculations from previous theories
for the mechanism that assumes first order kinetics
for both Ag+, Agz+ [i. e., from Eq. (68)] are shown in
these figures as well (dashed line) and they show little
agreement with the data. This is particularly true in
Fig. 6 where the shape of the prediction from the pre-
vious theories for the first order mechanism does not
have the same shape as the data. Thus one can see why
Gordon and Wahl found it necessary to abandon this
mechanism.
From the point of view of statistical rate theory then,
so far as one can tell from the data given, there is no
reason to abandon the mechanism of Eq. (79), but it
is the rate expreSSion that assumes first order in each
reacting component, i. e., Eq. (2), that should be
abandoned.
VII. SUMMARY AND CONCLUSIONS
(1) In the preceding development, the formalism of
quantum mechanics is used to obtain the expreSSion for
the probability of a system undergoing a change in mo-
lecular distribution corresponding to a single step of a
chemical reaction in an element of time, This formal-
ism does not require that the path by which the system
makes the change in distribution be specified. One only
considers the molecular distribution before and after
the step. From the expression for this probability the
statistical rate theory approach is used to obtain the
expression for the net rate of the chemical reaction.
The form of the expression is that of a product of the
equilibrium exchange rate Kx with a factor ariSing from
nonequilibrium effects that is ultimately expressed in
terms of the chemical potentials of the products and re-
actants. H under equilibrium conditions, the exchange
rate for a reaction vanishes; then the reaction rate is
zero at all times; thus non equilibrium effects do not
create a reaction but they only accelerate it in one di-
rection or the other.
To determine the value of the equilibrium exchange
rate one must consider a speCial case and specify the
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mechanism by which the exchange rate is established;
however, since it is the equilibrium exchange rate one
can take advantage of the substantial simplifications
that become available in the equilibrium state.
(2) The expression for the rate of the chemical reac-
tion may be written in terms of the concentrations and
the equilibrium exchange rate by conSidering a special
case and making use of the expressions for the chemical
J
potentials. For the case of a reaction between ions in
solution one finds that the concentration dependence of
DB 0.9 the reaction rate is different than that predicted by ab-
solute rate theory or any of the previous theories, with
the statistical rate theory expression predicting a higher
rate during the initial period.
When the statistical rate theory expression is exam-
ined in the near-equilibrium limit, it is found to reduce
to the same concentration dependence as used in previous
theories and an expression is obtained for the conven-
tional rate constant k in terms of quantities ariSing from
the statistical rate theory approach.
To evaluate the expreSSion obtained for the conven-
tional rate constant, a dilute electrolyte system is con-
sidered and it is assumed that in equilibrium the ions
fluctuate between associated ion pairs and free ions.
When the derived expreSSion for the conventional rate
constant is evaluated for this system, the well known
empirical relation between the ionic strength and the
conventional rate constant (called the Brpnsted primary
salt effect) is obtained.
(3) To examine the prediction of a higher reaction rate
during the initial period made from statistical rate the-
ory, this approach was applied to examine the electron
exchange reaction between ions in solution. Data avail-
able in the literature that gave the concentration as a
function of time for six different experiments was ex-
amined. This data was obtained by Wahl and his co-
workers using radioactive labeling techniques for vana-
dium, manganate-permanganate, and silver.
According to statistical rate theory, Kx should be con-
stant for these experiments. After integrating the the-
oretical expreSSion for the reaction rate and chOOSing
the value of K" to be that which gives a minimum total
error between the theory and experiment, one finds
that there is no measurable disagreement between the
theory and experiment for five of the six cases examined,
and that the disagreement is small for the other case.
This general agreement exists throughout the experi-
mental period, even in the period initially after the re-
actants are brought together.
This is in contrast to the results obtained from pre-
vious reaction rate theories. All of these have the same
concentration dependence. They all disagree with the
data in the initial period. To obtain agreement in this
period, it has become conventional to introduce the con-
cept of zero-time exchange. This amounts to adding a
constant to the relation expreSSing the concentration as
a function of time that is obtained by integrating the rate
expressions. Although adding this constant does lead
to agreement between the calculations and the measure-
ments except in the case of silver, the zero-time ex-
 C. A. Ward: Effect of concentration on chemical reactions
change has not been explained on a physical basis. In
the case of silver, even the addition of the zero-time
exchange was not sufficient to obtain agreement between
the previous theories and the experimental data. It
was necessary to suggest a change in mechanism.
From the point of view of statistical rate theory, it
is unnecessary to introduce the concept of zero-time
exchange, since the predictions are in agreement with
the theory, even in the period immediately after the re-
actants are brought together; nor is there any need to
suggest a change in mechanism on the basis of the in-
formation presently available in the case of silver,
since there is agreement in this case as well.
This improvement in the agreement between the theory
and experiment (seen in Figs. 1-6) results from the con-
centration dependence of the rate expreSSion derived
from the statistical rate theory approach.
(4) We note that the agreement between the results
from the statistical rate theory approach and the avail-
able data for the rate of chemical reactions discussed
above is matched by the agreement between this theory
and the measured rate of gas absorption by a liquid, 19
and the measured rates of nondissociative13 and disso-
ciative18 adsorption of a gas on a solid surface. Thus
the statistical rate theory approach appears to lead to
an improved expreSSion for the rate of a broad range
of processes.
ACKNOWLEDGMENTS
I wish to thank Roger Parsons and Jacek Lipkowski
for reading the manuscript and for many helpful sug-
gestions; the Laboratoire d'Electrochimie Interfaciale
du CNRS, France for one year of residence and the Na-
tural Science and Engineering Research Council of
Canada for support of this work.
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