Seymour Lowell

C.W. Post College of

I'Hospital's Rule Applied to
Long lslond University
Brookville, L.I., N e w York Kinetic Equations

The differential equation describing a
second order reaction is
Where x is the concentration of products, a and b are
the initial reactant concentrations, k is the rate con-
stant and t is time.
The solution to equation (1) when a equals b is
and when a is not equal to b the solution becomes
and substituting a for b one obtains equation (2).
Another application of 1'Hospital's rule can be made
to a second order reaction accompanied by a first order
reaction producing the same products. An example of
this is the nucleophilic displacement of an alkyl halide
accompanied by solvolytic displacement. The rate
equation for this type of reaction is
where k, is the bimolecular rate constant and kz is the
solvolytic constant, The solution to equation (5) by
the method of partial fractions give

Students are often confused because substitution of a The term (a - x) can be substituted for (b - x) in equa-
for b in equation (3) does not yield equation (2). tion (6) only under the following two conditions: (1) kz =
Actually the value obt,ained is indeterminate since this O a n d a t t = O , a = b . Then(a-x)isequalto(b-x)

- a t all times; (2) k2 # 0 and a t t = 0, a > b. Then a t

substitution gives kt = 0/0. The form 0/0 suggests
using 1'Hospital's rule' in order to determine the limit
of equation (3) as b a.
Therefore,?
time t', (a - x) will equal (b - $)but beforeand after t',
(a - x) cannot equal (b - x). Since equation (6) ap-
plies a t all times, condition (1) is the only circumstance
that permits substitution of (a - a) for (b - x).
Therefore equation (6) becomes

Upon taking the derivative

since ka is zero, substitution gives the indeterminate
df(b)ldb
~ --
form, t = 0/0 and again applying I'Hospital's rule one
ds(b)ldb
obtaim

1 L'I'Haspital'srule" is:
t = lim
_
.+.
(8)
- - l.m f'b)
k*+O d k*
lim f(2)
g(z)
7
Y (2) .+, After taking the derivative, simplifying,and substituting
See for example, STEPHENSON, G., "Msthematical Methods for kt = 0, the expression for a second order reaction with
Science Students," John Wiley & Sons, Inc., New Yark, 1961, initially equal is obtained
nn
FL-. - - -..
9697
In cases where a is near, but not equal to b, the method of
WIDEQ~EST, S., Arkiv Kemi,Z6A (1948), can be employed.

552 / Journol o f Chemical Education