ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT

cients for the cross flowmeter would have to be determined experimentally.

Nomenclature
= = f = g = AH =

literature Cited

orifice meter coefficient, dimensionless inside diameter, ft. Fanning friction factor, dimensionless local acceleration of gravity, ft./sec.$ meter differential, feet of fluid flowing K = velocity head coefficient, dimensionless AK = section 4 contribution to K due to pipe friction, dimensionless L = length, ft. R = meter differential, inches of carbon tetrachloride minus water Re = Reynolds number, dimensionless t = linear velocity of fluid, ft./sec.

(1) (2) (3) (4) (5)

(6)

(8) (9)
(10)

(7)

Chem. Eng., 60, No. 3, 124 (1953). Gentile, V., Jr., U. S.Patent 2,260,019 (Oct. 21, 1941). Hoopes, J. W., et al., Chem. En#. Progr., 44, 691 (1948). ENG.CHEM., 37, 588 Kroll, A. E., and Fairbanks, H. T., IND. (1945). Lansford, W. M., Ureiu.Illinois Eng. E x p t . Sta., Bull. 289 (1936). Lapple, C. E., Chem. Eng., 56, No. 5, 96 (1949). Nord, M., Ibid., 57, Ko, 7 , 113 (1950). Perry, J. H., Chemical Engineers Handbook, p. 377, New York, McGraw-Hill Book Co., 1950. Ibid., p. 415. Steams, R. F., et al., Flow Measurements with Orifice Meters, New York, D. Van Kostrand Co., 1951.

RECEIVED for review May 22, 1953.

ACCEPTED January 22, 1954. Presented before the Regional Conclave of t h e A M E R I C A N CHEMICAL SOCIETY, Kew Orleans, La., Deo. 10-12, 1953.

Kinetics of Coupled
GERARD

N. VRIENS

American Cyunumid Co., Bound Brook, N. J

kinetically like a system of coupled-i.e., consecutive, or parallel-first-order, reversible reactions. This may be so even if the reactions are truly second order, provided that either one reactant is present in considerable excess or its concentration is maintained a t a constant level throughout the reaction. In still other cases reactions of more complex order may be represented empirically with sufficient accuracy by the first-order equations. Even when a quantitative representation of the reaction kinetics is not given by the simpler first-order equations, considerable insight into the reaction mechanism may often be obtained from them. This is particularly advantageous when, as is the case with coupled reversible reactions, an exact mathematical solution of the kinetics of higher ordered reactions is generally not possible. The system of coupled, first-order, reversible reactions is one of the most complex kinetic systems to be capable of exact mathematical analysis. Solutions for the case of consecutive reactions have been given ( I , 2, 4, 6); unfortunately, in tyro cases they contain errors (2, 6). Furthermore, the solutions referred to are complex and difficult to apply. The case for parallel reactions does not appear to have been solved. The purpose of this paper is to present the solutions to this important kinetic system for both consecutive and parallel reactions in a form which is simplified for ready application by the use of dimensionless ratios and groups. These equations, in the form given, have been conveniently and successfully applied to the study of several commercial reactions in these laboratories. The special conditions under which the kinetics of parallel reactions resemble those of consecutive reactions are discussed in detail.
Dimensionless Groups and Ratios Are Employed To Develop Solutions for First-Order Rate Equations

ANY chemical proccsses of industrial importance behave

2
where
5

k,x - ksy - kay + k4z

r + y + z = l
= mole fraction of mixture present as A a t time t = mole fraction present as B at time 1

y
z

= mole fraction present kl = specific rate constant kz = specific rate constant k3 = specific rate constant ka = specific rate constant

as C a t time t for conversion for conversion for conversion for conversion

of of of of

A to B B to A B to C C to B

Equations 1 to 4 can be solved simultaneously to give the following second-order differential equations:

(5)
d2z

+ (kl + kz + ka + ka) 2 + (kik + kzka + kika) z

dz

kika
(6)

Consider the following system of equations:

A &BaC kz k4
Then

ki

k3

@
dt

= kzy -

klx

Solutions to Equations 5 and 6 will be given under the boundary conditions imposed by the t a o most important cases, that of consecutive reactions in which case the starting material consists entirely of A and that of parallel reactions in which case the starting material consists entirely of B. Case I. Consecutive Reversible Reactions. Consecutive reversible reactions are commonly encountered in practice as, for example, in the case of alkylations in which 2 moles of alkylating agent react successively with the substrate. If the alkylating agent is present in excess or is maintained a t a constant concentration, or pressure, the first-order equations may be expected to apply. Of course, in such a case the pseudo equilibrium constants for the first-order reactions will be a function of the particular concentration of alkylating agent used. The equations for consecutive, firsborder, reversible reactions were first solved and discussed in detail by Lowry and John (4). Solutions have also been presented, in slightly different forms, by Frost and Pearson ( I ) , Sherwood and Reed (6), and Hougen and Watson ( 2 ) . I n the case of the latter two references, errors in

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ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT

sign occur in several of the formulas for the constants of integration. These discrepancies ma>- bc observed by comparing the formulas given in this paper with those in the references cited. I n all of these prior solut,ions, from two to four reaction rate constants appear in the final equations, thue making them estrrmely awkward to apply t o actual reaction rate studies. I n the follo.il-ing solutions these constants have been completely eliminated. Before solving Equations 5 and 6 it is desirable to simplify the constants. Although the four reaction rate constant. will vary wit,h the process variables, it is usually true that ratios of these constants are relatively independent of th(3 temperature, catalyst, etc. For esample, k l / k 2 and k3/k4 represent equilibrium constants which are completely independent oi' the catalyst, and, in most cases, nearly independent' of the temperature over the narrow temperature ranges normally of commercial interest. Similarly, the ratio of t,he forward rat? constants for the two reactions, 1;3/kl: may be expected to h t comparatively constant over varying reaction conditions, provided the consecutive reactions are of the same general t>.pp. Equations 5 and 6 may be rewritten as follows:

In order to use these equations it if necessary to determine the values of the three constants, K I ,K z ,and a. The two equilibrium constants may easily be evaluated by making a single run under conditions such that a close approach to equilibrium is attained and then measuring the resulting ratios of the three c*omponents. The value of a may be estimated by experimentally determining the variation of composition as the rea~tion proceeds. If y has a maximum, which will be true whenever cu <K?, then the problem is simplified to finding that value of a xhich, when substituted in Equations 11 and 12, will give thi. same maximum for 1-2-8. As a first approximation the relatioriship, ymaS. = N which holds for consecutive irreversiblc reactions. map frequently be convenient to use. After the constants have been evaluated, a plot may bc constructed of 5, y, and z versus e from Equations 4, 11, and 12. This graph will be characte ic of t,he reaction system unt1i.r. consideration and essentially independent of the process conditions. From the composition of a given reaction product, the corresponding value of 6' may either be read from the plot or calculated from Equations 11 or 12. Rl- dividing 6' by the time of reaction t,he value of t,he rate constant, kl, may be determind and used to characterize the rate of reaction under the particular conditione used. Thus, the effect of the process variables on the reaction rate may be studied directly in spite of the fact that four different rate constants appear in the general solution to the kinetic equations. Case 1 1 . Parallel Reversible Reactions. Parallel reversi1)k reactions occur most frequently in the case of substitution rc:l'-tions in which two isomers may be formed-for esample, in certain sulfonations. First-order kinetics may apply i f the sulfonating agent is present in large excess: if it is continually fortifie:l, or if the water of reaction is removed continuously. Although the pseudo equilibrium constants for the first-order reactioria will be a function of the strength of the sulfonating agent, the equilibrium between the tn-o isomers is independent of this variable. By making substitutions of the same general type as were made in Case I, Equations 5 and G may be converted to the following form, in which all of the rate const,antshave been eliminated:

u-here

I<:

= =

k 1 / k 2 = equilibriuni constant for the formation of B

Icy
cI

from A k J k 4 = equilibrium conptant for the formation of C from B = k3,'k, = ratio of forward rate constants for t h e consecutive reactions

All but one of the reaction rate constants have been eliminatctl If the final substitution of % = h ~ is t made in Equations 7 and 8 the resulting equations take the f o ~ m
d2X

de? -

+(]+K+"+&i

.Ir

There 6 = a measure of the extent of approach t o equilibrium. A11 of the terms of Equations 9 and 10 consist of dimensionless ratios or groups and every constant is essentially independent of the r e a d o n conditions, including the reaction rate. The boundary conditions for this case are, when e = 0: x = 1; 0 dx - = -1 , @ d B = 0 . Using standard methods for solving 2
d6

linear differential equations with constant coefficients, t,he following solution may be obtained:

where

IC3

e
670

from R = k , / h z = ratio oi. forward rate constants for the parallel reactions
=
Ic2t

ki/'kl = equilibrium constarit for the formation of

i l

INDUSTRIAL A N D ENGINEERING CHEMISTRY

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ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT

The boundary conditions for this case are when 6 = 0, x = 0,
2

1oi
08

= 0,

dx
~

dB = 1,

CiZ

2 6

p.

On applying these conditions to the

i:
- Consecutive
- - Parallel
6

where

c.
a

P I+m3 __0 3 - Da

0 0 w 0 1

------2
I

io

Figure 1.

Comparison of Kinetics of Hypothetical Systems of Consecutive and Parallel Reactions

As was true in Case I, only three constants, K,, Ks. and @-all relatively independent of reaction conditions-must be known in order to use Equations 15 and 16 and to construct a graph of 2, y, and z versus e. The equilibrium constants may again be determined by an equilibrium run, and the value of p is best calculated by extrapolating the ratio of the reaction products obtained a t low conversions back to zero conversion. The value of 6 corresponding to a given reaction product may be divided by the time of reaction to give a value of the rate constant, kz, which may then be used as a measure of the reaction rate.
Kinetics of Parallel Reactions Resemble Those of Consecutive Reactions under Special Conditions

Under certain conditions the kinetics of reversible parallel reactions are similar to those of consecutive reactions. This is true when the product-e.g., isomer-which is formed more rapidly is the less stable thermodynamically. Under these circumstances this product will initially increase to a maximum and then gradually be replaced by the other product. The effect is as though it were the intermediate in a series of consecutive reactions, whereas actually the transformation of one product into the other involveb first a reversal of the reaction bv which the former was formed. This situation is illustrated by Figure 1, in which the kinetics of two hypothetical systems of consecutive and parallel reactions are compared. The solid lines represent consecutive reactions; the data were obtained by solving Equations 4, 11, and 12 for a = 0.30, K1 = 9.45, and Kz = 1.246. The broken lines represent parallel reactions and were obtained by solving Equations 4, 15. and 16 where p = 0.40, K Z = 100, and K B = 4.65. I n view of the general similarity of the two sets of curves, it is not surprising that controversy has frequently appeared in the literature over which mechanism applies in a given case. A good method of distinguishing between the two cases in such a situation is to study the reaction a t a very low

range of conversions. I n Case I1 (parallel reactions) the ratio of the two products will be nearly constant over this range, while in Case I this ratio r i l l change rapidly. A classical example is the monosulfonation of naphthalene in 13 hich a-naphthalenesulfonic acid, the predominating product duiing the early stages of the reaction, is gradually replaced by the beta isomer as the reaction proceeds. In a brilliant paper, Lantz (3)demonstrated qualitatively that the conversion of the alpha to the beta sulfonic acid takes place by a desulfonationresulfonation mechanism rather than by a direct isomerization. The solutions presented in the present paper for parallel reversible reactions show quantitatively how this type of transformation may take place and give mathematical support to the intuitive concepts of Lantz. Another example is the dialkylation of benzene, in which the ortho and para derivatives that form the predominant product a t low temperatures or with mild catalysts are converted to the more stable b u t less rapidly formed meta isomer under more *were reaction conditions. I t is generally agreed that this transformation involves dealkylation-realkylation and, therefore, it may be expected that if the ortho and para isomers are treated AS a single compound the equations for parallel reversible reactions may also be applied to this case. Undoubtedly, many other reaction systems exhibit this type of behavior and it is hoped that the equations presented will be of some value in studying the kinetics of such systems. The equations derived in this paper are valid only for batch ieactions or for continuous reactions in long tubular reactors and do not hold for continuous stirred tank reactors.
Acknowledgment

The review and suggestions of R. H. Wilhelm of Princeton University are gratefully acknowledged.
literature Cited
(1) Frost, A. A ,
p.

(2)
(3)

(4)
(5)

and Pearson, R. G., Kinetics and Mechanism, 162, New York, John Wiley & Sons, 1953. Hougen, 0. A., and Watson, K. >I., Chemical Process Principles, p. 831, New York, John Wiley & Sons, 1947. Lantz, R., Bull. SOC. chim., 2, 2092 (1935). Lowry, T. M., and John, W. T., J . Chem. SOC., 97, 2634 (1910). Sherwood, T. K., and Reed, C. E., Applied Mathematics in Chemical Engineering, p. 110, New York, McGram-Hill Book Co., 1939.

RECEIVED for review October 16, 1953. ACCEPTED February 1, 1954. Presented before the Industrial and Engineering Group at the Meeting-inf the North Jersey Section of the AMERICAN CHEMICAL SOCIETY, Miniature o Jan. 2 5 , 1954.

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