Exp 4-Rate Law

1
EXPERIMENT 4: DETERMINING RATE OF REACTION BY THE EFFECT OF

CONCENTRATION AND CATALYST

Objectives:
To determine the rate of reaction (reaction order) of KMnO
4
and H
2
C
2
O
4
by the
effect of concentration and catalyst.
To learn about the kinetics of chemical reaction.
To learn about rate law.

Introduction:
There are many factors that affect the speed of a chemical reaction, some of the
more common ones being concentration effects, temperature effects, surface area and
catalysts. In this experiment, two variables that will affect the reaction rate will be studied
that are concentration effects and catalysts. An increase in the concentration of the
reactants often increases the speed of a reaction. If two molecules, A and B must collide in
order to react, anything that increases the frequency of those collisions increases the rate
of the reaction. Increasing the concentration of a reactant most often results in an
increased reaction rate as the molecules are closer together so collisions can occur more
frequently. Catalysts dramatically speed up a chemical reaction by allowing the reaction to
proceed via a much easier (energy wise) pathway or by giving the reaction a sort of short
cut to follow.

In this laboratory the Rate Law for the reaction between potassium permanganate
(KMnO
4
) and oxalic acid (H
2
C
2
O
4
). The chemical equation of this reaction is as following:
3 H
2
C
2
O
4(aq)
+ 2 KMnO
4(aq)
6 CO
2(g)
+ 2 MnO
2(s)
+ 2 KOH
(aq)
+ 2 H
2
O
The rate of this reaction was easily measured because the permanganate ion is bright
purple and the only other colored species in the system is manganese dioxide (MnO
2
),
which is a golden yellow in solution. Thus, all the permanganate ion had reacted away
when the purple color fades and was replaced by a golden yellow. The faster the purple
color of the permanganate fades, the faster the reaction was occurring.

2

The Rate of Reaction for any general reaction: a A + b B c C + d D can be
defined in terms of any of the observable species involved in the reaction:
Rate of reaction =

Because t is large, it was the time required for all the permanganate ion to disappear, so
actually the average rate of reaction over the reactions time course was measured.
Rate of reaction =
. The factors such as concentration and catalysts will not

affect the rate of all chemical reactions, but at least some will affect any given reaction.
And, occasionally, odd factors, such as such the amount of dust present in the reaction
vessel, will also affect the rate.

While knowing the rate of a reaction after the reaction was completed, it provides
some information, in order to predict how altering a variable will change the reaction rate,
the rate law for the reaction need to be determined. A Rate Law is an equation that directly
relates the concentration of the reactants to the speed of the reaction when all other
conditions, such as temperature, pressure, etc were held constant. For a reaction A+B
C, the general rate law would be: Rate = k[A]
m
[B]
n
. These exponential variables are called
reaction orders and were found experimentally through a series of experiment called the
method of initial rates. In this experiment, the Rate Law for the reaction will have a simple
form: Rate = k [H
2
C
2
O
4
]
m
[KMnO
4
]
n
where m and n are the orders of the reaction with
respect to H
2
C
2
O
4
and KMnO
4
, respectively.

A brief overview of this experiment is oxalic acid was added into the conical flask
containing KMnO
4
which was mix thoroughly using the magnetic bar and magnetic stirring
hotplate. The time taken for the solution to turn yellowish was recorded. In part I, the
concentration was set differently by diluting with different amount of water whereas in part
II different amount of catalyst H
2
SO
4
was used. The rate constant, and order with respect
to each reactants and overall order were then calculated.

Materials & Apparatus:
3

KMnO
4
(0.02M), H
2
C
2
O
4
(0.5M), H
2
SO
4
, conical flask, magnetic bar, magnetic stirring
hotplate, stopwatch

Procedures:
Part I: Determining the rate of a chemical reaction effect of concentration
1) The reagents were prepared as tabulated in table below:
Reagents Experiment 1 Experiment 2 Experiment 3
H
2
C
2
O
4
(mL) 150 150 100
KMnO
4
(mL) 10 5 30
H
2
O (mL) 0 5 30

2) The required amount of KMnO
4
was placed in a thoroughly washed and dried conical
flask. The magnetic stirring bar was placed into the conical flask.
3) The oxalic acid was added into the conical flask containing KMnO
4
and the timing was
started once the beaker containing oxalic acid was emptied.
4) The mixture was mixed thoroughly by swirling the conical flask or magnetic stirring
hotplate.
5) The swirling or stirring was continued until the solution turned a light yellow or brown
color.
6) The timing was stopped and the time it actually took for the reaction to take place was
recorded.
7) Steps 2-6 were repeated for experiments 2 and 3.
8) The rate for each of the 3 experiments was determined.
9) The full rate equation for each experiment was written out.

Part II: Determining the rate of a chemical reaction effect of catalyst
1) The reagents were prepared as tabulated in table below:
Reagents Experiment 1 Experiment 2
H
2
C
2
O
4
(mL) 100 100
KMnO
4
(mL) 30 30
H
2
SO
4
(mL) 10 2
4

2) The required amount of KMnO
4
was placed in a thoroughly washed and dried conical
flask. The magnetic stirring bar was placed into the conical flask.
3) The oxalic acid and sulphuric acid were added into the conical flask containing KMnO
4

and the timing was started once the beaker containing oxalic acid was emptied.
4) The mixture was mixed thoroughly by swirling the conical flask or magnetic stirring
hotplate.
5) The swirling or stirring was continued until the solution turned a light yellow or brown
color.
6) The timing was stopped and the time it actually took for the reaction to take place was
recorded.
7) Steps 2-6 were repeated for experiments 2 and 3.
8) The rate for each of the 3 experiments was determined. Remember this was just the
[KMnO
4
] / t
average

9) The full rate equation for each experiment was written out.

Results & Discussion:
Part I:
Data collection:
Experiment 1 Experiment 2 Experiment 3
Molarity of KMnO
4
(M) 0.02 0.02 0.02
Molarity of H
2
C
2
O
4
(M) 0.5 0.5 0.5
Volume of KMnO
4
(mL) 10 5 30
Volume of H
2
C
2
O
4
(mL) 150 150 100
Volume of H
2
O (mL) 0 5 30
Time taken (s) 195 215.4 235.8

Calculations:
Experiment 1 Experiment 2 Experiment 3
Concentration of
KMnO
4
(M)
1.25 x 10
-3
6.25 x 10
-4
3.75 x 10
-3
5

Concentration of
H
2
C
2
O
4
(M)
0.4688 0.4688 0.3125
Average time (s) 195 215.4 235.8
Initial rate for
KMnO
4
(M/s)
6.1403 x 10
-6
2.9016 x 10
-6
1.5903 x 10
-5

Sample calculation:
1) Concentration of KMnO
4

M
1
V
1
= M
2
V
2

M
2
= M
1
V
1
/ V
2

M
2
= (0.02)(10) / 160
= 1.25 x 10
-3
M
#

2) Concentration of H
2
C
2
O
4

M
1
V
1
= M
2
V
2

M
2
= M
1
V
1
/ V
2

M
2
= (0.5)(150) / 160
= 0.4688 M
#

3) Average time

= Time taken (since only one trial was conducted for each experiment)
= 195 s
#

4) Initial rate for KMnO
4

r = [KMnO
4
] / t
average
= 1.25 x 10
-3
M / 195 s
= 6.4103 x 10
-6
M/s
#

5) Find the order with respect to KMnO
4
and H
2
C
2
O
4

(I) Order with respect to KMnO
4

6

0.4526 = 0.5
m
m log 0.5 = log 0.4526
m = 1.1437
#

(II) Order with respect to H
2
C
2
O
4

5.4808= ()
()

0.6666
n
= 0.9135
n log 0.6666 = log 0.9135
n = 0.2231
#

6) Find the overall order for this reaction,
Overall order = m + n
= 1 + 0
= 1
#

7) Find the rate constant, k for this reaction,
By using experiment 1,

= k (
()

k = 5.1282 x 10
-3
s
-1

#
7

In part I, based on the result and calculation, it was shown that from experiment 1 to
experiment 3, as the concentration of reactants decreases, the time taken for the reaction
increases and the rate of reaction also decreases from experiment 1 to experiment 3.
Therefore, it can be summarized that the rate of reaction increases with concentration of
reactants. Amongst the experiments, the reaction during experiment 1 (highest
concentration of KMnO
4
that is 1.25 x 10
-3
M) had the highest rate of reaction that was
6.4103 x 10
-6
M/s and it taken the shortest time for reaction that was 195s.
According to the collision theory, the rate of a reaction is directly proportional to the
number of effective collisions per second between the reactant molecules. Effective
collision is the fraction of total collisions that actually result in the formation of the
product(s). If the concentration of the reactants increases (i.e. particles per given volume)
the greater the number of total collisions. The greater the frequency of total collisions, the
greater the frequency of effective collisions. If the frequency of effective collisions
increases, so does the reaction rate. (N.a., n.d.)
By comparing two experiments using initial rate and concentration of both KMnO
4

and H
2
C
2
O
4
, it was determined that this reaction is first order with respect to KMnO
4
and
zero order with respect to H
2
C
2
O
4
. Hence, the overall order of reaction is first order. The
value of k constant also being determined that was 5.1282 x 10
-3
s
-1
.
Part II:
Reagents Experiment 1 Experiment 2
H
2
C
2
O
4
(mL) 100 100
KMnO
4
(mL) 30 30
H
2
SO
4
(mL) 10 2
Time taken (s) 3.05 3.12

1) Why does it take so much longer for the color of the solution in the beaker on the
right (experiment 2) to change?
The time taken for the color of the solution in the beaker on the right to change
is longer because the amount of catalyst used (H
2
SO
4
) is lesser. Catalysts are
8

substances used to speed up the rate of reaction without being consumed. As
the amount of catalysts used is lesser, the rate of reaction of experiment 2 is
lower, thus it takes a longer time to change color.

2) Write a balanced chemical equation for the reaction of permanganate ion and oxalic
acid to give Mn
2+
and carbon dioxide. The reaction takes place in an acidic solution.
2MnO
4
-
+ 5 H
2
C
2
O
4
+ 6H
+
2Mn
2+
+ 10CO
2
+ 8H
2
O

3) The reaction in the beaker on the right eventually proceeded at a reasonably rapid
rate. Explain how this observation supports a reaction mechanism involving
autocatalysis.
In autocatalysis, the reaction is catalyzed by one of its products. Initially, the
reaction is very slow at room temperature. The reaction is then catalyzed by
manganese (II) ions. There obviously aren't any of those present before the
reaction starts, and so it starts off extremely slowly at room temperature.
However, from the equation, it was found that manganese (II) ions amongst
the products. More and more catalyst is produced as the reaction proceeds
and so the reaction speeds up. (Jim.C., 2010)

Conclusion:
The rate of reaction increases with increasing concentration of reactant. The rate of
reaction also increases with increasing amount of catalysts used. The reaction between
H
2
C
2
O
4
and KMnO
4
is first order with respect to KMnO
4
, zero order with respect to H
2
C
2
O
4
.
The overall order for the reaction is one and the rate constant, k is 5.1282 x 10
-3
s
-1
.

Safety Precaution:
Oxalic Acid is poisonous. Gloves must be wearing when handling solutions
containing oxalic acid. If some spills on skin, rinse it off with copious amounts of
water. Large spills require flushing with water for 15 minutes.
Permanganate is a strong oxidizing agent. The solutions of permanganate must be
handled with gloves.
9

Limitations of experiment:
There was a human limitation to make sure that the final color of solution was same
for all 3 experiments. In some samples the color of the reaction had gone past the
color of what the comparison was so then the time recorded of the reaction would be
recorded as taking longer.

References:
Jim.C. (2010) Autocatalysis. [Online]. Available from: http://www.chemguide.
co.uk/physical/catalysis/introduction.html. [Accessed: 30 September 2013].
N.a, (n.d.) Determination of the Rate Law for the Oxidation of Oxalic Acid by
Permanganate. [Online]. Available from: http://infohost.nmt.edu/~jaltig/OxalicAcid
Kinetics.pdf. [Accessed: 30 September 2013].
N.a. (2013) Determining the rate law. [Online]. Available from:
http://www.chm.uri.edu/dfreeman/chm192/expt2_2013.pdf. [Accessed: 30
September 2013].
N.a. (n.d.) Chemical Kinetics---Determining the Rate Equation. [Online]. Available
from: http://www.chem.umass.edu/genchem/chem112/112_Experiment_3.htm.
[Accessed: 30 September 2013].
N.a. (n.d.) Kinetics: Factors affecting reaction rates. [Online]. Available from:
http://www.chem.tamu.edu/class/majors/tutorialnotefiles/factors.htm [Accessed: 3
October 2013].

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1

EXPERIMENT 4: DETERMINING RATE OF REACTION BY THE EFFECT OF

. The factors such as concentration and catalysts will not

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