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University of Cincinnati, Cincinnati, Ohio

INTEACHING chemical kinetics, the conducting of a

suitable quantitative demonstrative experiment is
often something of a problem. Preliminary prepara- Rearranging and integrating without limits yields
tion of solutions, standardization, and carefully timed
titrations are usually required. To circumvent these
difficulties an analogous kinetic experiment involving Equations 1 and 2 are exactly analogous to those for
a physical process can be performed which is much a firstorder irreversible chemical reaction where the
simpler and yet which clearly demonstrates the prin- rate of decrease in the concentration of the reactant
ciples involved in a first-order reaction. - d c / d s is proportional to the concentration itself, or,
The analogy is based on Poiseuille's law for the vis-
cous flow of fluids. According to this relationship the
rate of flow for a given liquid a t constant temperature
through a capillary of given dimensions is proportional A similar integration of equation 3 without limits yields
to the pressure drop across the capillary. Where this
pressure drop is due solely to gravity head in a reservoir
of constant horizontal cross section, the rate of fall in The similarity between the two sets of equations, and
height, - d H / d r for the liquid level in the reservoir, be- therefore the analogy between the two types of kinetic
comes proportional to the height of the level itself, or, phenomena, is obvious. The gravity-head driving

force in the first set corresponds t o the concentration

driving force in the second set. Thus a simple demon-
stration involving a falling liquid level can be employed
to illustrate a kinetic "reaction."
The equipment required consists of an ordinary 50-
ml. buret, clamped vertically in the usual manner, with
a 6-inch length of capillary tubing connected to its tip
with rubber tubing. The capillary is clamped in posi-
tion so that its free end is a t the same level as the 50
ml. mark on the buret, as shown in Figure 1. The
buret is filled with water a t room temperature, partially
drained to force out air, and refilled above the 0 ml.
mark. The stopcock is then opened wide and the
liquid level allowed to fall. The time is noted as the
level passes half a dozen or so well-spaced ml. marks.
By subtracting these ml. readings from 50 ml. a measure
of the height of the liquid level is obtained for various
instants. Plotting these heights against the elapsed
time on semilogarithmic coordinates yields a straight
3 u
0 1 2 3 4
Time in minutes
5 6 7

Fi- 2. Rate of Change in Xquid L-1

line from which k ' may be determined, thus demon-

strating the validity of equations 1 and 2 and therefore
by analogy also equations 3 and 4. Figure 2 shows a
plot of such experimental data.
The analogy may be extended even further. For
example, the temperatnre of the water may he in-
creased, thus decreasing its viscosity and in turn iu-
creasing k'. For moderate changes in temperature,
the logarithm of the viscosity is linear with the recipre
cal absolute temperature 1/T. By combining this fact
with Poisenille's law it can he shown that the logarithm
of k ' itself is linear with 1/T. This is analogous to the
situation for a chemical reaction where, according to
the integrated form of the Arrhenius equation for
moderate changes in temperatnre, the logarithm of
the velocity constant k is also linear with 1/T. I n this
manner the effect of temperatnre on reaction rate may
be demonstrated.
Another extension of the principle involves the use
of two burets in series, the first feeding the second, and
the second feeding the receiver. This represents two
consecutive chemical reactions. The initial rise, at-
tainment of a niaximum, and subsequent fall of the
liquid level in the second buret is analogous t o the
initial increase, attainment of a maximum, and sub-
sequent decrease in the concentration of the inter-
mediate compound. Thus the principles involved in
a series reaction may he demonstrated.
I n conclusion, it might be pointed out that these
experiments not only aid in the teaching of chemical
kinetics as such, but serve t o introduce the student to
some aspects of the fundamental similarities between
the kinetics of chemical and physical processes.