Experiment 4 : Kinetics : Order of Reaction

Objective :

To determine the order of reaction

Introduction :

The dependence of a reaction on concentration and order of reaction is described by a rate

law that has the following form :

Rate = k[A]x[B]y[C]z

Where k is the rate constant, x is the order of reaction with respect to reactant A, y is the order
of reaction with respect to reactant B, z is the order of reaction with respect to reactant C and []
represents concentration in moles per liter. The sum of x, y and z is known as the overall order
of reaction. Even though temperature is not included in the rate law, it plays an important role
in the rate of reaction so it must be held constant during a kinetic experiment. The rate of a
reaction must be determined experimentally and it cannot be determined by looking at the
balanced chemical equation.

The reaction under investigation is between permanganate and oxalic acid. Potassium
permanganate is deep purple in colour and after reacting it will change to a light brown colour
so this reaction can be monitored visually. The rate of reaction can be expressed as

Rate = k[KMnO4]x[H2C2O4]y

In order to determine the speed of the reaction, focused on the permanganate and simply
equate the speed with the time it takes to use up the permanganate.

Rate = -d[KMnO4] / dt = -｛[KMnO4]final - [KMnO4]initial｝/ ( tfinal - tinitial)

Since [KMnO4]final = 0, and if [KMnO4]initial is set = 0, the above equation simplifies to :

Rate = -(-[KMnO4]initial / tfinal) = [KMnO4] /t

The method of initial rates will be used to find the exponents x & y. This method involves
measuring and comparing the intial rates of a reaction when different initial concentrations are
used. The initial rate for each being the potassium permanganate concentration divided by
time. There is an assumption made here that is not always valid : tfinal will be measured to
determine each rate. Foe experiment 1 and experiment 2, the rate expressions can written as

Rate1 = k[KMnO4]1x[H2C2O4]1y Rate1 = [KMnO4]1 /t1

Rate2 = k[KMnO4]2x[H2C2O4]2y Rate2 = [KMnO4]2 /t2

Taking the ratio of the two rates :

Rate1/Rate2 = ([KMnO4]1 / [KMnO4]2)x

(Note that in these two reactions [H2C2O4]1 = [H2C2O4]2 and thus can be canceled out)

Thus, we can determine x. In a similar manner, y, the order of reaction with respect to oxalic
acid can be determined if compared experiments 1 and 3.

Procedure :

1. Three burettes were set up, one containing KMnO4 (~0.02M), one with H2C2O4 (~0.5) and
one with distilled water. A label was placed on each. The exact molarities of the KMnO4 and
H2C2O4.

2. The required amount of H2C2O4 and water was placed into a thoroughly washed and dried
conical flask according to Table 4.1. The amounts were dictated by the experiment that was
carried out. If overshoot, started again. This lab was very dependent on dispensing the exact
quantities.

Table 4.1 Volume of reagents required

Reagents Expt 1 (cm3) Expt 2 (cm3) Expt 3 (cm3)

H2C2O4 20.00 20.00 10.00

KMnO4 10.00 5.00 10.00

 H2O 0.00 5.00 10.00

3. The required amount of KMnO4 was placed into a test tube.

4. The permanganate was added to the oxalic acid and the timing was started when the
permanganate tube was emptied. The solution was mixed thoroughly by swirling the conical
flask and the swirling was continued until the solution turns to light yellow/brown colour. The
timing was stopped and the time it actually took for the reaction to take place was recorded.

5. Step 4 was repeated with a second and third trial. The average of those three was taken as
the reaction time.

6. Steps 3 was repeated through 5 for experiments 2 and 3.

7. The rate for each of the three experiments was determined. Remember this is just the
[KMnO4] / taverage.

8. The values of k, x and y were determined.

9. The full rate equation for the reaction wwere write out. Noted that

Rate = k[KMnO4]x[H2C2O4]y
Calculation :

Initial rate1 = Volume / taverage

= 30.00 cm3 / 4.14 min

= 7.25 cm3/min

Initial rate2 = Volume / taverage

= 30.00 cm3 / 5.07 min

= 5.92 cm3/min

Initial rate3 = Volume / taverage

= 30.00 cm3 / 8.49 min

= 3.53 cm3/min

Order of reaction

Rate = k[KMnO4]x[H2C2O4]y

Rate1 = [KMnO4]1 / taverage.

= 6.67×10-3 M / 4.14 min

= 1.61×10-3 M/min

Rate2 = [KMnO4]2 / taverage.

= 3.33×10-3 M / 5.07 min

= 6.57×10-4 M/min

(Rate1) / (Rate2) = (k[KMnO4]1x[H2C2O4]1y ) / (k[KMnO4]2x[H2C2O4]2y )

(1.61×10-3M/min) / (6.57×10-4M/min) = (k[6.67×10-3M]1x[0.33M]1y ) / (k[3.33×10-3M]2x[0.33M]2y)

21 = 2x
 x=1

Rate1 = [H2C2O4]1 / taverage.

= 0.33 M / 4.14 min

= 0.080 M/min

Rate3 = [H2C2O4]3 / taverage.

= 0.167 M / 8.49 min

= 0.0197 M/min

(Rate1) / (Rate3) = (k[KMnO4]1x[H2C2O4]1y ) / (k[KMnO4]3x[H2C2O4]3y )

(0.080 M/min) / (0.0197 M/min) = (k[6.67×10-3M]1x[0.33M]1y ) / (k[6.67×10-3M]3x[0.167M]3y)

22 = 2y

y=2

Rate = k[KMnO4]1[H2C2O4]2

Overall order = 1 + 2

= 3rd

Rate constant

Rate1 = k[KMnO4]1x[H2C2O4]1y

1.61×10-3 M/min = k[6.67×10-3M]11[0.33M]12

k = (1.61×10-3 M/min) / ([6.67×10-3M]11[0.33M]12)

= 1 M2min-1

Discussion :

The experiments are conducted based on the rate equation: Rate = k[KMnO4]x[H2C2O4]y,
where k is the rate constant while x and y are the reaction orders of KMnO4 and H2C2O4
respectively. As reaction orders, x and y is defined as the power to which the concentration of
that reactant is raised to in the experimentally determined rate equation. The reaction is first
order with respect to [KMnO4] and second order with respect to [H2C2O4]. The overall rate
order is 3. It was observed that the rate of reaction increases with increasing
concentration. The Collision Theory explains the phenomenon by stating that for a chemical
reaction to occur, reactant molecules must collide together in the proper orientation and the
colliding molecules must possess a minimum energy known as the activation energy, E A,
before products are formed. An increase in the concentration of reactants leads to an increase
in the number of reactant molecules having energy ≥ E A, hence increasing the collision
frequency. The increase in the effective collision frequency leads to an increase in the reaction
rate. When performing a chemical kinetics experiment, the procedures have to be conducted
at a constant temperature. According to the Arrhenius equation, k=Ae-Ea/RT, a slight increase in
temperature increases reaction rate significantly as the equation is exponential in nature. This
is affirmed by the Maxwell-Boltzmann distribution curve as a slight increase in temperature
increases the number of colliding particles with Ea and consequently, reaction rates
significantly. Hence, because slight deviations in temperature may affect reaction rates
significantly, the temperature at which the experiment was carried out must be kept constant.
To prevent errors from occurring, all glassware used in this experiment must be kept clean and
dry to prevent contamination by the previous batch of experimental products. The overall
volume of the solution was also kept constant at 30 mL by adding distilled water to standardize
the conditions of the reaction environment, thus increasing accuracy. Swirling of the conical
flask contents for the same length of time must be done consistently so that results obtained
will be fair. Instead of swirling with one’s hands, the conical flasks can be placed on an
electronic swirl to ensure consistent swirling when conducting the experiment. Also, there is
inaccuracy as the stopwatch was stopped only when an arbitrary colour intensity was
observed. There should be a consensus between lab partners as to when the stopwatch
should be stopped.

Conclusion :

From this experiment, the rate equation of the chemical reaction is Rate = k[KMnO4]x[H2C2O4]y
where rate constant k is 1 M2min-1. The reaction is first order with respect to [KMnO4] and the
reaction is second order with respect to [H2C2O4]. The overall order of reaction is 3.
Questions :

1. In this experiment, the orders of reaction x and y are obtained by taking ratios of rates for
two trials or experiments.

a) Explain how this experiment can be modified so that the orders of reaction can be
obtained by plotting appropriate graphs.

A measure of the rate of the reaction at any point is found by measuring the slope of the graph.
The steeper the slope, the faster the rate. Since we are interested in the initial rate, we would
need the slope at the very beginning. Now the experiment suppose to be done again with a
different (lower) concentration of the reagent. Again, the time taken for the solution to turn
yellow/brown colour was measured and so we are still just looking at the very beginning of the
reaction.

b) What plots must be done and explain how the orders of reaction can be determined from
the plots?

Plot 1/t as a measure of rate against the varying concentrations of the reactant that were
investigating. If the reaction is first order with respect to that substance, then it should get a
straight line. That's because in a first order reaction, the rate is proportional to the
concentration.If a curve was obtained, then it isn't first order. It might be second order.

c) Would this method (grphically) be more accurate than what has been done
experimentally?

It shows that analytical method is more accurate, precise and efficient compared to graphical
method of analysis. These two methods of analysis areboth important but only one is more
efficient and accurate.

2. Orders of reaction are normally integers. Is it possible to have non-integers e.g fractions as
order of reaction? If yes, give an example of such reaction.
Reaction order can be zero, an integer or non-integer. A reaction rate can have a negative
partial order with respect to a substance. For example the conversion of ozone (O3)
[O3 ]2
to oxygen follows the rate equation r = k in an excess of oxygen. This corresponds to
[O2 ]
second order in ozone and order (-1) with respect to oxygen.