CHM 431 - PHYSICAL CHEMISTRY

EXPERIMENT 4

KINETICS : ORDER OF REACTION

ALLOCATED MARK % MARK %

Objectives of the 1
experiment

Introduction 3
Experimental procedure 3
Results and Observations 4
Calculations 4
Discussion 4
Conclusions 1
Questions 4
References 1
TOTAL 25

NAME : ROBIATUL ADAWIYAH BINTI ROSLAN (2016675066)

COURSE : RAS 245 2B

DATE OF EXPERIMENT : 27 / 9 / 2016

DATE OF SUBMISSION : 4 / 10 / 2016

LECTURER’S NAME : PROF. MADYA SHUKRI BIN ISMAIL

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 OBJECTIVE:

To determine the order of a reaction.

INTRODUCTION:

By doing experiments involving a reaction between A and B, you would find that the rate of the
reaction was related to the concentrations of A and B in this way:

This is called the rate equation for the reaction.

The concentrations of A and B have to be raised to some power to show how they affect the rate
of the reaction. These powers are called the orders of reaction with respect to A and B. The
overall order of the reaction is found by adding up the individual orders. For example, if the
reaction is first order with respect to both A and B (a = 1 and b = 1), the overall order is 2. We
call this an overall second order reaction.

PROCEDURE:

1. Set up three burettes, one containing KMnO4 (0.02 M), one with H2C2O4 (0.5 M) and one
with distilled water. Place a label on each.
2. Into a thoroughly washed and dried conical flask, place the required amount of H2C2O4
and water according table 4.1. The amounts are dictated by the experiment that we are
doing.

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

H2C2O4 20 20 10
KMnO4 10 5 10
H2O 0 5 10

3. Place the required amount of KMnO4 into a test tube.

4. Add the permanganate to the oxalic acid and start timing when you have emptied the
permanganate tube. Mix thoroughly by swirling the conical flask and continue swirling
until the solution turns to light yellow / brown color. Stop timing and record the time it
actually took for the reaction to take place.

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 5. Repeat this with a second and third trial. Take the average of these three as the reaction
time.
6. Repeat steps 3 through 5 for experiments 2 and 3.
7. Determine the rate for each of the three experiments.

RESULT:

Solutions H2C2O4 KmnO4

Experiment 1 Molarity 0.5 M 0.02 M
Volume 20 cm3 10cm3
Concentration 10 cm3 0.2 cm3

Experiment 2 Molarity 0.5 M 0.02 M

Volume 20 cm3 5 cm3
Concentration 10 cm3 0.1 cm3

Experiment 3 Molarity 0.5 M 0.02 M

Volume 10 cm3 10 cm3
Concentration 5 cm3 0.2 cm3

Trial 1 Trial 2 Trial 3 Average Time

(min)
Expt 1 3.18 3.19 3.20 3.19
Expt 2 3.46 3.22 3.02 3.23
Expt 3 5.30 5.17 5.30 5.26

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 CALCULATION:

Concentration H2C2O4

molarity x volume

Experiment 1 : 0.5 M x 20 cm3 = 10 cm3

Experiment 2 : 0.5 M x 20 cm3 = 10 cm3

Experiment 3 : 0.5 M x 10 cm3 = 5 cm3

Initial rate of H2C2O4 . KmnO4 (Ms-1)

Molar / time in second

Experiment 1 : (0.5 M x 0.02 M) / 191.4 = 5.22 x 10-5 Ms-1

Experiment 2 : (0.5 M x 0.02 M)/ 193.8 = 5.16 x 10-5 Ms-1

Experiment 3 : (0.5 M x 0.02 M)/ 315.6 = 3.17 x 10-5 Ms-1

Order of reaction with respect to H2C2O4

r1 ( H 2C 2O 4) 1 ( KmnO 4) 1
r3 =[ ( H 2C 2 O 4) 3 ]m [ ( KmnO 4) 3 ]n

5.22 x 10−5 0.2 10

=
3.17 x 10−5 [ 0.2 ]m [ 5 ]n

1.6467 = 2n

lg 1.6467 = n lg 2

n = 0.7

≈1

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 Concentration KmnO4:

molarity x volume

Experiment 1 : 0.02 M x 10 cm3 = 0.2 cm3

Experiment 2 : 0.02 M x 5 cm3 = 0.1 cm3

Experiment 3 : 0.02 M x 10 cm3 = 0.2 cm3

Initial rate of H2C2O4 . KmnO4 (Ms-1)

Molar / time in second

Experiment 1 : (0.5 M x 0.02 M) / 191.4 = 5.22 x 10-5 Ms-1

Experiment 2 : (0.5 M x 0.02 M)/ 193.8 = 5.16 x 10-5 Ms-1

Experiment 3 : (0.5 M x 0.02 M)/ 315.6 = 3.17 x 10-5 Ms-1

Order of reaction with respect to KmnO4

r1 (H 2C 2 O 4) 1 ( KmnO 4)1
r2 =[ (H 2C 2 O 4) 2 ]m [ ( KmnO 4)2 ]n

5.22 x 10−5 10 0.2

=
5.16 x 10−5 [ 10 ]n [ 0.1 ]
m

1.0116 = 2m

lg 1.0116 = n lg 2

m = 0.01

≈0

Rate constant

Rate = k [KmnO4]m [H2C2O4 ]n

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 5.22 x 10-5 = k [0.02]0.01 [0.5]0.7

K = 8.8 x 10-5 s-1

DISCUSSION:

The experiments are conducted based on the rate equation, R = k [KmnO4]m[H2C2O4 ]n,
where k is the rate constant while x and y are the reaction orders of KmnO4and 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. X and y cannot be
found theoretically and are experimentally determined to be 1. This means that the reaction is
zero order with respect to [KmnO4] and first order with respect to [H2C2O4 ]. The overall rate
order is 1. This reaction is said to be bimolecular since two reactant species are involved in the
rate determining step.

It was observed that the rate of reaction of KmnO4 decreases with increasing
concentration. In contrast, the rate of reaction of H2C2O4 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, EA, before
products are formed. An increase in the concentration of reactants leads to an increase in the
number of reactant molecules having energy ≥ EA, 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.

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

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 colour intensity was observed. There should be a consensus between lab partners as to when
the stopwatch should be stopped.

CONCLUSION:

The rate equation of the chemical reaction between KmnO4and H2C2O4 has been found to be:

R = k [KmnO4]0 [H2C2O4] where rate constant, k = 8.8 x 10-5 s-1

The reaction is zero order with respect to [KmnO4]and the reaction is first order with respect to
[H2C2O4]. The overall order of reaction is 1. This reaction is said to be bimolecular since two
reactant species are involved in the rate determining step.

QUESTIONS:

1. In this experiment the orders of reaction m and n 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.
Modifying this experiment by determination of integrated law.

b. What plots must be done and explain how the orders of reaction can be
determined from the plots?
The straight line graph is plotted concentration against time. The slope of each
group is the determination of order of reaction.

c. Would this method (graphically) be more accurate than what has been done
experimentally?
Yes. Because the slope is more accurate to determine the order reaction.

2. Orders of reaction are normally integers. Is it possible to have non-integers example

fractions as order of reaction? If yes, give an example of such reaction.

The order of a reaction is not necessarily an integer. The following orders are possible:

 Zero: A zero order indicates that the concentration of that species does not affect the
rate of a reaction
 Negative integer: A negative order indicates that the concentration of that species
INVERSELY affects the rate of a reaction.

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 Positive integer: A positive order indicates that the concentration of that species

DIRECTLY affects the rate of a reaction.
 Non-Integer: Non-integer orders, both positive and negative, represent more intricate
relationships between concentrations and rate in more complex reactions.
REFERENCES:

Chemical kinetic. (2014). Kanpur, India: Chandralok Prakashan.

Islamova, R. M., Kolesov, S. V., & Zaikov, G. E. (2011). Kinetics, catalysis & mechanism of
chemical reactions: From pure to applied science. Hauppauge, NY: Nova Science.

Logan, S. R. (1996). Fundamentals of chemical kinetics. Essex, England: Longman.

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