Solving Differential Equations in Kinetics by Using Power Series

Elvln Hughes, Jr.

Southeastern Louisiana University, Hammond, LA 70402

This article descrihes an approach for solving eq 2, a dif-

ferential equation that arises in the discussion of a set of
consecutive chemical reactions that are outlined in eq 1.

These coefficients form a series in k l and kz and can, in

general, be represented by the following series:
Kl and K z are first-order rate constants. The differential
equation representing the change in the concentration of
species B with respect to time is the following: where

[&I is the initial concentration of component A, and [B] is Thus, the power series solution introduces another series
the concentration of species B. The solution to this equation that must he resolved in order t o calculate the coefficients.
is ordinarily materially inadequately presented in textbooks Equation 9 can he rewritten as
and provides very little to instruct students how to solve
differential equations. This article descrihes a series solution S, = k," + k,"-'k, + k1"-2k,2 + . ..+ klk2"-' (10)
for the equation and covers the following two objectives: If one divides hoth sides of the equation by k l and multiplies
a . 1)escribeageneral method for sohing differentia!equations, and by kz, one obtains
b. Provide background for solving drfierentia! equations, whrch can
later be extended in quantum mechanics.
S,k,lkl = kl"-'k, + k,"-'k,2 + . ..+ k,kZn-' + k," (11)
Now, subtract eq 11 from eq 10 to obtain
The solution t o eq. 2 can he expressed as a power series, in
time, by the following equation: S, - S,k,lk, = k," - k," (12)
Rearrangement of eq 12 leads to
where a, is the coefficient of the time t, raised to the nth S, = k,(k," - kz")l(k,- k 2 ) (13)
power. The initial boundary condition is [B] = 0 a t t = 0. Substitution of eq 13 into eq 8 leads us to the following
Immediately, this implies that an is equal to zero. With this
set of conditions, differentiating eq 3 and expressing Lk1'as a, = (-l)""[A,,]k,(k," - k,")l[(k, - k,)n!] (14)
a power series, eq 2 becomes or
Xna,tn-' = kl[A,,]X(-l)"k,"t"ln! - k,Xo,t" (4) a, = (-l)"[A,,lkl(kl"- k,")l[(k, - k,)n!] (15)
where where -1 was factored from the denominator in eq 14. Final-
e?' = X(-l)"kl"t"ln! ly, eq 15 can he substituted into the original power series
expansion in eq 3 and with this one obtains the following:
By comparing the coefficients of tn-' on hoth sides of eq 4,
[Bl = E(-l)"[Aolk,(k," - kp")tnl[k2
- k,)n!] (16)
one obtains the following recursion relationships for the
coefficients: This series is now immediately recognizable as the expan-
na, = kl"[A,,](-1)"-'l(n-1) - kza,_, (5) sion of (e-'I' - eLbat).With this in mind, we arrive at the
solution, eq 17, frequently given in physical chemistry text-
or booksl.
a . = k,"[A,](-1)"-'In! - k,a._,h (6) [B] = [ ~ , ] k , ( e ~-"eCkz')l(kz
~ - k,) (17)
Several of the coefficients, a,, are given by the following
equations:
a, = 0
' Alberty. Robert A. Physical Chemistly, 7ih ed.; Wiley: New York.
a, = k@ol 1987; p 691.

46 Journal of Chemical Education