Consistency between Kinetics and Thermodynamics

2889

measure efficiencies of energy transfer processes from various bath gases. It is especially important that these studies be extended to higher pressures to obtain E," and the energy barriers to the decomposition of gaseous ions, since this is a quantity of great importance in ion chemistry. Acknowledgments. This research was supported in part by a grant from the National Science Foundation. We thank Mr. R. Ciccarone for performing many of the measurements reported in this paper.

References and Notes

(1) P. J. Robinson and K. A. Holbrook, "Unimolecular Reactions", Wiley-lnterscience, London, 1972. (2)F. H. Field, J. Am. Chem. SOC., 91, 2827 (1969). (3)(a) J. J. Solomon, M. Meot-Ner, and F. H.Field, J. Am. Chem. SOC., 96, 3727 (1974): Detailed description is given in M. Meot-Ner, Ph.D. Thesis, The (b) Rockefeller University, New York, N.Y., 1975. (4)M.Meot-Ner and F. H. Field, J. Chem. Phys., 64, 277 (1976).

(5) P. Ausloos and S. G. Lias in "Ion-Molecule Reactions", Vol. 11, J. L. Franklin,

Ed., Plenum Press, New York, N.Y., 1972,p 707. (6)F. P. Lossing, private communication. (7)A. Flaux, B. Wirtz, and T. Gaumann, Helv. Chim. Acta, 57, 525 (1974). (8)R. P. Wayne, in "Comprehensive Chemical Kinetics", C. H. Bamford and D. F. H. Tipper, Ed., Elsevier, New York, N.Y., 1969,p 270.

Consistency between Kinetics and Thermodynamics

M. Boudart
Department of Chemical Engineering, Stanford University, Stanford, California 94305 (Received February 6, 1976)

If an expression is known or postulated for the rate of a chemical reaction in the forward direction, what are the thermodynamic restrictions on the form of the rate expression for the reverse direction? Is there a relationship between rate constants in both direction and the equilibrium constant of the reaction? This question has been considered by a number of but perhaps with a lack of generality or rigor. The purpose of the present note is to take advantage of work by T e m I ~ i nthat bears directly on this problem to clarify a sit~,~ uation which is of great practical interest. Consider a sequence of s steps, open or closed, the sum of which represents a stoichiometric equation for reaction proceeding a t a net rate r. If the rate of each step is denoted by r, in the forward direction and by r-, in the reverse direction, with i = 1 , 2 , . , . , s, we can write the identity:

Now, for every elementary process and its reverse which have rates r, and r-l amenable to the equilibrium formulation of transition state theory, we can write:

r,/r-l = exp(A,/RT)

(6)

where A, is the affinity of step i in the forward direction, equal to -AG;, the Gibbs free energy of reaction. With (6), (5) becomes

(7)
Now, the average stoichiometric number of the reaction E is defined, following Temkin,7 as

( r 1 - r-1)r2r3 . . . r,

r-lr-z(r3

+ r-l(i-2 - r - 2 ) ~ . . r, . - r - 3 ) . . . r, + . . , + r-lr-2r-3. . . (r, - r-s) - r1r2r3. . . r, - r - l r - z r - 3 , . . r-, (1) ( i = 1 , 2, . . . ,s )

(2)

where A is the total affinity for the overall reaction

At the steady state, we may write

rL-r-,=x,r

where x , is the stoichiometric number of step ia6 Substitution of (2) into (1)yields Ternkin's general equation for the rate of a single reaction at the steady state: rlr2i-3.. . r, - r-lr-2r-3. . . r.-, r= x l r z r , ~. .. r,? r - 1 ~ 2 r 3. . . r, . . . r-1r-2 . . . x,

I have shown elsewhere6 that jj retains its meaning a t equilibrium. Substitution of (8) into (7) yields the relation equivalent to (6) but applicable to a single reaction instead of an elementary step:
i / F = exp(A/ERT)

(10)

(3)

If any step from left to right is irreversible (r-i = 0), the reaction is proceeding irreversibly from left to right a t a rate r = i. Similarly, if any step i s irreversible when it proceeds from right to left ( r , = 0), then r = r'. From (3),we get then
i: =
(rlrzr3.

It must be noted that X depends on composition and, therefore, may change withextent of reaction. If there exists a rate-determining step (subscript 1 ) so that A, N 0 except for i = 1, it is clear that F = x1, and eq (10) becomes

i l F = exp(A/xl/RT)
whereas eq 5 simplifies to
i / F = rl/r-l

(11)

. . r,)/P and F = (r-lr--2r-3. . . r-s)/P

(4)

where P is the denominator of eq 3. Thus

(5)

(12)

since ri r-1 except fori = 1. Equation 11due to Horiuti2is a particular case of Temkin's eq 10.
The Journal of Physical Chemistry, Vol. 80, No. 26, 1976

2070

M. Boudart

There is little incentive to go beyond the statements of eq 10 and 11. Both express, with rigor and generality, the expected consistency between thermodynamic requirements and kinetic formalisms. Indeed since r = i - F or r = i [ l- (?/?)I, we must have for any acceptable rate law:

The function cp, like the polynomial P of eq 4,may be a function of both temperature and concentration. Then, eq 1.8 becomes, with substitution of (19) and (20)
(KIk)
+ -

j=1

n (Bj)"-", = Kl/%[
c

(Bj)-*]lii

(21)

r = ?[l- exp(-A/F/RT)]

(13)

The expression between brackets can be considered as a thermodynamic potential f a ~ t o r . ~ However, because of previous results in the literature, it is useful to show that, with certain reasonable assumptions, eq 10 gives

j$/h = KlK

(14)

where K is the equilibrium constant of the overall reaction and k and 12 are suitably defined, overall rate constants for the forward and reverse rates of the single reaction. Indeed, from thermodynamics

Now on the left-hand side, h/k is a function of temperature only, while the product is a function of concentrations only if the orders of reaction are "good" orders, Le., they do not depend on temperature. On the right-hand side, Kl'x depends only on temperature, at least in a field of compositions where j7 is approximately constant, whereas the product depends only on composition, a t least if is a "good" average stoichiometric number, Le., is independent of temperature. Therefore:

(j$/k)(K-I/%) =

fi ( B
j=1

J . ) [ - ( ~ ' J / X ) - ~ ~ / + ~ , I=

constant

(22)

A = A" - R T In

]=I

fi (BJ)ui

(15)

where A" is the standard affinity for the reaction

O=

j=1

C ujBj

(16)

where uI is the stoichiometric coefficient of component B, in the stoichiometric equation for reaction between c components, counted as positive for a product and negative for a reactant. The concentration of BJ in the thermodynamically ideal system is ( B J ) Besides . A"=RTlnK Substitution of (15) and (17) into (11)gives
j=1

(17)

where the constant is a pure number which must be unity, since for (22) to be true for arbitrary values of the independent concentrations, all exponents of the concentrations must be equal to zero. Hence, we can write eq 14 within the approximations mentioned. This is the general form of a relation which many authors have written in different ways, as an expression of the consistency requirement between kinetics and thermodynamics. Its obtention from Temkin's general equation in the form of (18) is trivial. Nevertheless, it may clarify some obscure or less general statements in the literature.1-6 If the system is thermodynamically nonideal, all concentrations should be replaced by activities and klk may now contain some activity coefficients of transition states which are composition dependent but only slightly so compared to the exponential temperature dependence of the rate constants. Thus within that additional approximation, the result expressed by eq 14 above remains valid. References and Notes
(1) K. G. Denbigh, "The Principles of Chemical Equilibrium", University Press, Cambridge, 1961, p 442. (2) J. Horiuti, J. Catal., 1, 199 (1962). (3) E. H. Bium and R. Luus, Cbem. Eng. Sci., 19, 322 (1964). (4) p. Aris, "Elementary Chemical Reactor Analysis", Prentice Hall, Englewood Cliffs, N.J., 1969, p 56. (5) P. Van Rysselberghe, Chem. Eng. Sci., 22, 706 (1967). (6) M. Boudart, in "Physical Chemistry: An Advanced Treatise", Vol. 7, H. Eyring, W. Jost, and D. Henderson, Ed., Academic Press, New York, N.Y., 1975, Chapter 7, p 353. (7) M. I. Temkin, Dokl. Akad. Nauk SSSR, 152, 156 (1963). (8) M. I. Temkin, int. Cbem. Eng., 11, 709 (1971). (9) J. Happel, Catal. Rev., 6, 221 (1972).

(18)

Now, let us assume, as is found frequently in catalytic reactions, that i and F can be expressed as follows:

where and are functions of temperature only, Ctj and LU, are orders of reaction which may be positive, negative, or zero.

The Journal of Physical Chemistry, Voi, 80, No. 26, 1976