OBJECTIVE:

1) To determine the order of a reaction.

APPARATUS:

1) Burette
2) Conical flask
3) Test tube
4) Stop watch

CHEMICALS:

1) 0.020 M Potassium Permanganate ( KMnO4)

2) 0.50 M Oxalic acid ( H2C2O4 )

PROCEDURE:

1) Three burettes were set up , one contained KMnO4 ( ~0.02 M ) , one with H2C2O4 ( ~0.5
M ) and one with distilled water. Label were placed on each. It is difficult to visually
differentiate between water and oxalic acid. The exact molarities of the KMnO 4 and
H2C204 were recorded.
2) Into a thoroughly washed and dried conical flask , the required amount of H 2C2O4 and
water ( if any) according to table 4.1 were placed . The amounts was dictated by the
experiment that we are doing. If overshoot start again. This was very dependent on
dispensing the exact quantities.
3) The required amount of KMnO4 was placed into a test tube.
4) The permanganate was added to the oxalic acid and timing was started when we have
emptied the permanganate tube. The mixture was mixed by swirling the conical flask and
was continued swirling 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) This step was repeated with a second and third trial. The average of these three have been
taken as the reaction time.
6) Steps 3 through 5 were repeated for experiments 2 and 3.
7) The rate for each of the three experiments was determined. This is just the [KMnO 4 ] / t
average

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

9) The full rate equation for the reaction was determined.

RESULT AND CALCULATION:

1) The initial molarity:

KMnO4: 0.5M
H2C2O4: 0.02M

2) The volumes used : 30 mL

3) The final molarity:
H2C2O4:
M1V1= M2V2
(0.5M)(20.00) = (M2)(30.00)
M2= 0.3M

KMnO4:
M1V1= M2V2
(0.02M)(20.00) = (M2)(30.00)
M2= 0.007M

H2C2O4 KMnO4
Experiment 1 0.3M 0.007M
Experiment 2 0.3M 0.003M
Experiment 3 0.17M 0.007M
4) The average time for each experiment:
 (3.17s + 3.18s + 3.16s)/3 = 3.17s

Experiment The average time (s)

1 3.17s
2 2.49s
3 4.33s

5) The initial rate:

Rate = [KMnO4]/taverage
Experiment 1: 0.02/3.17s = 6.3091× 10^-3 mol/L.s
Experiment 2: 0.02/2.49s = 8.0321× 10^-3 mol/L.s
Experiment 3: 0.02/4.33s = 4.6189× 10^-3 mol/L.s

6) The order of reaction:

Experimen Initial Rate (mol/L.s) H2C2O4 (M) KMnO4 (M)

t
1 6.3091× 10^-3 mol/L.s 0.33 0.007
2 8.0321× 10^-3 mol/L.s 0.33 0.003
3 4.6189× 10^-3 mol/L.s 0.17 0.007

Order of H2C2O4: rate 1/ rate 3 = [H2C2O4]/[H2C2O4]

0.33/0.17 = 6.3091× 10^-3 mol/L.s/ 4.6189× 10^-3 mol/L.s
1.9412y = 1.3659
y = log 1.3659 / log 1.9412
y=1
Order of KMnO4: rate 2/ rate 1 = [KMnO4]/[ KMnO4]
0.003/0.007 = 8.0321× 10^-3 mol/L.s/ 6.3091× 10^-3 mol/L.s
0.4286x = 1.2730
x = log 1.2730 / log 0.4286
x=0
The rate of reaction: k [KMnO4]0 [H2C2O4]1
7) The overall order of this reaction is : x+y = 0+1 = 1
8) The rate constant: rate = k [KMnO4]x [H2C2O4]y
 k = rate/ [KMnO4]x [H2C2O4]y
Experiment 1: k = 6.3091× 10^-3 mol/L.s/ [0.007]0 [0.33]1
k = 0.0191 mol/L.s
Experiment 2: k = 8.0321× 10^-3 mol/L.s/ [0.003]0 [0.33]1
k = 0.0234 mol/L.s
Experiment 3: k = 4.6189× 10^-3 mol/L.s / [0.007]0 [0.17]1
k = 0.02717 mol/L.s

DISCUSSION:
From this experiment, the dependence of the reaction on concentration and order of
reaction is had been determine by rate law which is rate =k [KMnO 4]x [H2C2O4]y. The
reaction rate can be influenced by many factors. In the experiment it only study how the
concentration of reactant effect the reaction rate. When the concentration of the reactant
increase the speed of the reaction will be increase and if the concentration was decrease the
speed of the reaction will be also decrease. It is because the increase in the concentration
reactant will cause molecular collisions occur more frequently in the result an increase the
rate of reaction.

For this experiment, the rate of disappearance of one reactant had been monitor,
potassium permanganate, KMnO4, by monitoring the loss of the purple colour according to
the following reaction.
KMnO4(aq) + H2C2O4(aq) Mn2+(aq) + CO2(g) + H2O(l)
(purple) (colorless)
Rate of reaction = -∆[KMnO4]/∆T = -∆[ H2C2O4]/∆T = +∆[ Mn2+]/∆T
When all of the purple color is gone, the reaction is finished and the final concentration of the
KMnO4 is now zero. Since the initial time for ∆T is zero, the equation for the initial rate of
potassium permanganate is rate = [KMnO4]/taverage.
In this experiment, three experiment had been carried out by using three different
concentration of the reactant. The experiment 1 and 2 the concentration of oxalic was
maintained which is 0.33M. But the different concentration of the potassium permanganate
 was used which is 0.007M and 0.003M and the give the difference in the initial rate of the
reaction which is 6.3091× 10^-3 mol/L.s for experiment and 8.0321× 10^-3 mol/L.s for
experiment 2. For the experiment 3 the concentration of the oxalic was change to 0.17M and
the concentration of potassium permanganate was 00.07M and the initial rate is 4.6189× 10^-
3 mol/L.s.

By using the initial rate of the reaction the order of the reaction had been determined
which is the order for potassium permanganate is 0. Meanwhile, the order for oxalic acid is 1.
The overall order for this reaction is 1 and the rate constant for all of the experiment is
0.0191mol/L.s , 0.0243 mol/L.s and 0.02717 mol/L.s

CONCLUSION:
From this experiment, the order of the reaction had been determine which is the order for
potassium permanganate is 0 and the order for oxalic acid is 1. The overall order for this
reaction is 1.

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 the 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 is not first order. It might be second order.

c) Would this method 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 are both important but only
one is more efficient and accurate.

d) 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.
 Yes, reaction ,mechanisms are often complex. In cases where they can be reasonably
approximated by a power law, it is certainly possible to get fractional orders because at
the point it is just a matter of data fitting. As an example, the pyrolysis of acetaldehyde
(CH3CHO ) into methane and carbon monoxide proceed with an order of 1.5 with
respect to acetaldehyde.

REFERENCES :
1) Petrucci et al. General Chemistry : Principle & Modern Applications, 9 th Edition. New
Jersey : Prentice – Hall Inc.,2007.
2) Kenneth.C Chemical Kinetics : The Study of Reaction Rates in Solution. New York City
: VCH Publishers, Inc,.1990.