Chemical Engineering Science, 1973, Vol. 28, pp. 601405.

Papmoo

Press.

Printed in Great Britain

Self-adjoint operators from selected nonsymmetric matrices: application to kinetics and rectiiication
D. RAMKRISHNA Indian Institute of Technology, Kanpur 16, U.P., India and NEAL R. AMUNDSON University of Minnesota, Minneapolis, Mum. 55455, U.S.A. (Received 1 May 1972; accepted 8 June 1972) AMIt is shown that two problems, one which has become a classic in chemical kinetics developed by Wei and Prater and the other a more prosaic development in multicomponent rectification, when cast in the proper mathematical framework become amenable to a more direct solution. This involves the.selection of the proper inner product on a tlnite dimensional vector space so that the linear operators become selfadjoint. INTRODUCTION

as

as linear operators on the finite dimensional space R, or C,,. They also provide representations for linear operators defined on abstract finite dimensional inner product spaces [ 11.The matrix representation of a linear operator on an inner product space f depends on the nature of the inner product and the orthonormal basis set in 9. Self&joint operators obtain symmetric matrices as representations. The discussion here is restricted for the sake of convenience to real matrices. Further, the restriction to square matrices is obvious. Alternatively, symmetric matrices may be regarded as selfadjoint operators on R, in which the inner product between two elements in R,, x = (x,, x2, . . . . x,)andy= (yl,yz ,..., y,)isdefinedby

MATRICES act

(x9Y> =

glwjyj.

(2)

That (2) represents a valid definition satisfying the axiometric properties of an inner product is readily established. Consider an (n x n) nonsymmetric matrix T whose ijth element is tU. Define an operator T on R, such that for x E R,
TX = 2k

(3) (3a)

(TX), =j$ w,.

Cx9 Y) = i

f=l

xiYi.

Clearly T is not a self-adjoint operator if the inner product (1) is used. However, it would be interesting to ascertain if T is self-adjoint under the inner product (2) for some suitable positive (1) weights {rI, r,, , . ., r,,}. Let x, y E R,. Then (TX, Y)
- (x, TY) = = jgI ri 2 =$jg G.i(XJYi- XiY,) Gjri - trrr,1X,Yi (4) (5)

However, under suitable conditions to be determined presently, selected nonsymmetric matrices may generate self-adjoint operators. Self-adjoint operators are well-known to have certain desirable properties [ll. Suppose rl, r,, . . ., r, are positive numbers. Then a. new inner product between two elements x, y E R,, may be defined

where (5) follows from (4) by a switch of indices.

601

D. RAMKRISHNA and N. R. AMUNDSON

It is clear that (TX, Y) = b, TY) for every I, y E R, $and only if

titri = &r, (6)

The matrix K of rate constants has b for its #h element where the diagonal elements are given by

(8)
where the comma under the summation sign excludes j = i. The equilibrium moie fraction vector x* = (x:, r$, . . ., e) satisfies the equation Kx=o (9)

Thus the self-adjointness of T hinges on the availability of positive numbers r,, r,, . . ., r,, satisfying relationship (6). Once T is self-adjoint, the spectral theorem for compact operators becomes valid, which assures the existence of a discrete set of eigenvectors {A,, b, . . ., A,} and eigenvectors {zl, q, .). ., G} which form an orthonormal basis in R,[l]. The orthogonality of the eigenvectors is of course with respect to the inner product (2). The above approach has some interesting applications in chemical engineering. We present below two such examples. The advantage of the approach lies in its simplicity. Moreover, it is in keeping with the general theory of self-adjoint operators and may eliminate adhoc ways of dealing with such problems. The first example pertains to first order reaction systems and the second refers to multicomponent rectigcation.
FIRST ORDER REACTION SYSTEMS

which has only one independent solution since K has rank (n - 1). We take for granted the positivity of the components of x*. Since K is nonsymmetric, it should be evident that it cannot be a matrix representation of any self&joint operator on R, with the inner product (1). However, the principle of microscopic reversibility asserts that k+f = k&.
(10)

It is immediately evident that condition (6) may be satisfied if r, = l/x?. Thus we may define an operator K by
Kx=Kx x E R,. (11)

Wei and Prater 121have provided a penetrating analysis of first order reaction systems first treated by Jost [3]. Stated in algebraic terms, the dynamics of such systems are characterized by a nonsymmetric matrix K of rate constants. The incorporation of the principle of microscopic reversibility affords a symmetric matrix D similar to K so that several interesting properties of K such as real eigenvalues, negative-definiteness and weighted orthogonality of eigenvectors could be deduced from the properties of D. We shall demonstrate an alternative organization of this analysis in the light of preceding discussions. This analysis seems simpler and direct. Consider n species Al, A*, . . ., A, undergoing first order reactions represented by Al +A. (7)

In view of (10) K would satisfy the equality (Ra, b) = (a, Kb) (12)

for arbitrary a, b E R,, which implies the selfadjointness of K. That K is negative-definitive may be established from the sign of (13)

S.

(14)

In writing (14) we have used (8) and if we let

602

Self-adjoint operators from selected nonsymmetric matrices

k;j =b,i

#jand@

=Othen(14)becomes In (20) the summation indices r and k range from 1 to n. Using Eq. (10) Eq. (20) becomes

(15)
Similarly

(21)
Since z, is the rth eigenvector we have

The addition of (15) and (16) together with the use of (10) leads to Thus the rate constant ku is given by

(22)

(23) (17) which implies negative-definiteness of K. Thus all the eigenvalues of K are non-positive. Since K is self-adjoint its eigenvectors form an orthonormal basis in R,. Clearly A= 0 is an eigenvalue and the corresponding eigenvector is x*. That x* is a unit vector follows from the fact that IIx*II= (x*, x*) = Note that in (22) and (23) the summation index r runs from 2 to n because A1= 0. Equation (23) represents an immediate check of the equilibrium condition (10) since &f is symmetric with respect to interchanging i and j from the right hand side of (23). An interesting verification of (8) is obtained from (23) as follows. - $ &i = -+
J=l.i

i=l

gxp=1.

(18) $ &zi., i
r-2 J=l,i

zj,+.

(24)

There are n linearly independent eigenvectors x*(=x,), x-z,..., z, which form an orthonormal basis in R,. Thus

Employing (19), (24) becomes

which yields (8).

j=2,3,. - -, n.
MULTICOMPONENT RECTIFICATION

where z,..~ is the rth component of the eigenvector x,. It is the business of the experiments suggested by Wei and Prater[2] to obtain the eigenvalues {X,} and eigenvectors {z,} from straightline reaction paths starting from suitable initial conditions. In order to determine the unknown rate constants we let k, = (k,,, b, . . ., k,,,), j= 1,2,..., n, and expand 4 in terms of the orthonormal basis {z,} as below.

We will sidestep a preliminary discussion of this problem since it is available elsewhere [4]. The liquid and vapor compositions in the mth plate of a rectification column are related to a doctored variable vector X,,,= (XRI,l, Xna, . . ., X,,,,) which has n components originating from the n species in the multicomponent mixture. It is shown that X, satisfies the difference equation

603

D. RAMKRISHNA and N. R. AMUNDSON

where R, pf, xoj are the reflux ratio, volatility of species i relative to a key component (assumed independent of temperature), and composition of the ith species in the product respectively. The difference Eq. (26) must satisfy the initial condition
xO,f =

l=~A!&L
f A--&+

(34)

is obtained. This yields the eigenvalues from which the eigenvectors (21,%, . . ., z,) may aho be obtained. The original difference equation may now be written as x, = TX,-, &=P (26a) (27a)

Pi-

(27)

We define an operator T on R, as follows. For v = (u,, u,, . . ., u,J E R,

(Tvh = Rwr +pt 7

XOPI.

(28)

where p = Q1, p2, . . ., p,). This equation may now be solved in an elegant manner. Thus (X,, s) = (T&z-,, z,) = (L-I, =5(&-I, %) s). (35)

The operator T is obviously linear and the matrix representation of T using the basis (e,}, where ej= (0,O,..., O,l,O ,..., O)isthejthunitvector, is given by
t, = Rp&+pg-oj

8, =

I ,

; ; rj

(29)

Equation (35) is solved for the scalar variable (&, zj) subject to the initial condition (x0,5) = (P, x,) to obtain (JL s) = V%, zj) = Aj(p, z,). (37) (36)

which is clearly nonsymmetric. Thus T is not self-adjoint under the inner product (1). From visual inspection, it is clear that multiplication of tu by xoJpi yields a symmetric product. Thus

= q,,,R6, + x&o5 tfl3% Pi

(30)

and remains unaltered by interchange of indices i and j. Thus T is rendered self-adjoint under the inner product
(a, b) = $2 a&+ t31 )

Since (5) form an orthonormal basis in R,, X, is given by

Xm = 2

(Xrn, Z&ZJ= f:

&(P, S>S.

(38)

The eigenvalues of T may be obtained from (Tzh = Rpfz,+ pi 2 which yields (33) = pi E xojzj. j Multiplying (33). by xoi and adding over i the required characteristic equation (A-R&i
xojzj =

The calculation of the vapor and liquid compositions in the mth plate is a trivial step and is omitted since it is not relevant to the present discussion.
CONCLUSIONS

Al; -.

(32)
\--I

treatment of the above examples illustrates a neat and organized approach to the solution of linear finite dimensional problems involving nonsymmetric matrices under selected circumstances. The method outlined herein represents an effective way of isolating such circumstances.

The

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Self-adjoint operators from selected nonsymmetric

matrices

REFERENCES [l] LORCH E. R., The Spectral Theorem in Studies in Modern Analysis (Ed. BUCH R. C.). Prentice-Hall, Englewood Cliffs, N.J. 1962. [2] WEI J. T. and PRATER C. D., Advances in Catalysis, Vol. 13, p. 204. Academic Press, New York 1962. [31 JOST W., Z. Nnturforsch 1947 2a 159. [41 AMUNDSON N. R., Mathematical Methods in Chemical Engineering. Matrices and Their Application, Prentice-Hall, Englewood Cliffs, N.J. 1966.

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