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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

JOURNAL OF CHEMICAL EDUCATION

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

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.

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