CHEM 122L

General Chemistry Laboratory

Revision 2.1

Determination of the Rate Law for the Oxidation of Oxalic Acid

by Permanganate

To learn about the Kinetics of Chemical Reactions.

To learn about the Reaction Rate.
To learn about the Factors Affecting the Chemical Reaction Rate.
To learn about Rate Laws.

In this laboratory exercise we will determine the Rate Law for the reaction between
Permanganate (MnO42-) and Oxalic Acid (H2C2O4).
3 H2C2O4(aq) + 2 MnO4-(aq)
clear soln

6 CO2(g) + 2 MnO2(s) + 2 OH-(aq) + 2 H2O

purple soln

yellow colloid

(Eq. 1)

It is expected the Rate Law for this reaction will have a simple form:
Rate = k [H2C2O4]m [MnO4-]n

(Eq. 2)

where m and n are the Orders of the Reaction with respect to Oxalic Acid and Permanganate,
respectively. (We must keep in mind the Rate Law does not have to have this simple form.) It is
these reaction Orders we wish to determine.
The Rate of this reaction is easily measured because the Permanganate is bright purple and the
only other colored species in the system is Manganese Dioxide (MnO2), which is a golden
yellow in solution. Thus, all the Permanganate Ion has reacted away when the purple color fades
and is replaced by a golden yellow. The faster the purple color of the Permanganate fades, the
faster the reaction is occurring.
The Rate of Reaction for any general reaction:
aA + bB

cC + dD

(Eq. 3)

can be defined in terms of any of the observable species involved in the reaction:
Rate of Reaction =
=

(Eq. 4)

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=
=
In practice it is difficult to determine instantaneous concentration changes, so instead we
approximate the above definitions by:
in the limit t ~ small

Rate of Reaction =
=

(Eq. 5)

etc.

For our reaction, the observable species we wish to follow is Permanganate, so we define
the Reaction Rate as:
Rate of Reaction = - (1/2)

(Eq. 6)

Because t is large, it is the time required for all the Permanganate Ion to disappear, we
are actually measuring the Average Rate of Reaction over the reactions time course.
In general, the rate of reaction can depend on any number of factors, just as the rate of travel in
an automobile depends on the position of the accelerator or brake, hilliness of the ground, wind
speed, size of the engine, etc. In the case of a chemical reaction, the Rate can depend on:
Reactant Concentrations
Product Concentrations
Catalyst Concentration
Temperature
Amount of Light
Size of Heterogeneous Particles
etc.
These factors 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.
Typically, Reactant Concentration and Temperature are the major influences on the rate of
reaction. At a given temperature, the Rate of Reaction frequently depends on reactant
concentration according to a rather simple expression:
Rate = k [A]n [B]m

(Eq. 7)

where A and B are the reaction reactants. This form of the reaction rate dependence is known as
the Rate Law for the reaction and k is referred to as the Rate Constant. The reaction is said to
proceed according to Orders n and m. It should be emphasized the parameters k, n, and m must
be measured experimentally.

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For our reaction, the Rate Law will have a simple form such as this and this form is given in
Equation 2 above. It is the goal of this laboratory exercise to measure the Reaction Orders n and
m and thus determine the Rate Law for the Oxidation of Oxalic Acid by Permanganate.
So, how are the reaction orders for a chemical reaction measured? There are a number of
methods available. One of the most common is the Method of Initial Rates. In this procedure,
we selectively change the Initial Concentration of each Species and see how this change affects
the rate of reaction. Suppose we double the Initial Concentration of Species A and find it causes
the reaction rate to quadruple. We then know n = 2; or the reaction is Second Order in A. We do
the same with each subsequent Species suspected of influencing the rate of the reaction to
determine each Reaction Order. (Initial Rates are used in this methodology because they provide
a convenient reference point for comparing one trial against another. As mentioned above, for
our case, we will be using the reactions average rate.)
For an example, consider the following reaction:
NO2(g) + CO(g)

NO(g) + CO2(g)

We will assume the Rate of this Reaction is governed by a Rate Law of the following form:
Rate of Reaction = k [NO2]n [CO]m
In order to determine the Reaction Orders n and m, the following Initial Rate data has been
obtained:
Trial
1
2
3

Init. Rate (M/sec)

0.005
0.080
0.005

Init. [NO2] (M)

0.10
0.40
0.10

Init. [CO] (M)

0.10
0.10
0.20

In comparing Trials 1 and 2, we see a quadrupling of the initial NO 2 concentration cause the
Reaction Rate to increase by a factor of 16; 0.005 x 16 = 0.080. This means the Reaction Order n
= 2. The reaction is Second Order with respect to NO2. Now we compare Trials 1 and 3. Here a
doubling of the initial CO concentration causes no change in the Reaction Rate. Hence, the
Reaction Order m = 0 and the reaction is Zeroth order with respect to CO. Thus, the Rate Law for
this reaction is:
Rate = k [NO2]2

Thus, for our reaction, we need to selectively vary the concentrations of Oxalic Acid and
Permanganate and determine how the Rate of Reaction responds to these changes. The key to
determining the reaction orders is the ability to measure the reaction rate for each variation in
initial reactant concentration. And, as was noted above, this is simply a matter of determining
how fast the purple color of the Permangante fades.

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Pre-Lab Questions
1.

To determine the Reaction Order of the decomposition of Formaldehyde:

CH3CHO(g)

CH4(g) + CO(g)

which is assumed to proceed according to the following Rate Law:

Rate = k [CH3CHO]n
the following Initial Rate data has been obtained:
Trial
1
2

Init. Rate (M/sec)

0.76
1.4

Init. [CH3CHO] (M)

0.30
0.40

Use this data to determine the Reaction Order with respect to Formaldehyde.
Do this by comparing the Rate of Trial 2 to the Rate of Trial 1:
n

Because the Reaction Order does not have to be an Integer value, we should solve for n by taking
the logarithm of both sides:
log

= n log

and solving this algebraically for n.

Because the Reaction Order typically is an Integer value, we then round this experimentally
determined result to its closest Integer value. You should follow this procedure for this case.

What is the experimentally determined Reaction Order n for this decomposition reaction?
What is the approximate Integer value for n?
2.

For our reaction, the last reagent to be added to the reaction mixture is the Permanganate;
step 6 of the procedure below. The timing of the reaction starts "when half of the
Permanganate solution has been added to the test tube." This choice is arbitrary and could
be problematic. Under what circumstances could it be problematic?

3.

It is possible the Reaction Order is negative; for example consider the Rate Law for the
kinetics of the conversion of Ozone to Oxygen.
2 O3(g)

3 O2(g)

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rate = k [O3]2 [O2]-1

What are the implications for the reaction rate of a negative Reaction Order?

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Procedure
Stock solutions of each of the reagents are provided at the following concentrations:
[H2C2O4] = 0.755 M
[MnO4-] = 0.130 M
We will vary the initial concentration of the Oxalic Acid and Permanganate by varying the
volume of each reagent added to the reaction mixture. The concentration (volume) of only one
species will be varied from one experiment to the next so as to determine the influence of only
the species being varied. Because the endpoint of the reaction is difficult to determine, each
experiment will be performed in triplicate and the results will be averaged. Each experiment will
be prepared as follows:
Experiment

Oxalic Acid

Permanganate

Water

1
2
3

5.00
10.00
5.00

1.00
1.00
2.00

6.00
1.00
5.00

1.

Label a clean 100mL beaker:

Oxalic Acid
Obtain ~75 mL of Oxalic Acid solution and place it in the beaker. Oxalic Acid is
poisonous. Wear gloves when handling solutions containing Oxalic Acid. If some
spills on your skin, rinse it off with copious amounts of water. Large spills require
flushing with water for 15 minutes.

2.

Do the same for a beaker for Water.

3.

Label a clean 50 mL beaker:

Permanganate Ion
Obtain ~25mL of Permanganate and place it in the beaker. Permanganate is a strong
oxidizing agent. Handle solutions of Permanganate with gloves.

4.

Obtain a large test tube and clamp it in place over a stir plate. Add a small stir bar to the
test tube.

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(The Reaction Is Pictured Above After It Has Reached Its Endpoint.)

5.

Using pipets, add the Oxalic Acid solution and the Water to the test tube as specified for
Experiment #1 above. (Use a different pipet for each solution!) Turn on the stir plate and
allow the contents of the test tube to mix thoroughly. When adding the solutions to the
test tube, make sure the tip of the pipette is very close to the bottom of the tube.
Otherwise, some of the solution will stick to the sides of the tube and will not be a part
of the reaction mixture. Be sure to use good pipetting techniques as using poor
techniques will seriously degrade the quality of your data.

6.

Pipet the Permanganate solution into the test tube. Start the stopwatch when half of the
Permanganate solution has been added to the test tube. This must be done in one
quick addition. Again, you must be careful to use good pipetting techniques. This is
particularly important for the Permanganate solution. A single misplaced drop can
seriously affect the quality of the kinetic data.

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7.

Observe the solution over time. Stop the stopwatch when the last trace of the
Permanganates purple color disappears. The final solution will be a golden yellow with
some bubble formation due to the production of Carbon Dioxide gas by the reaction.
Determining the endpoint of the reaction is a bit subjective. (You may wish to perform a
sample trial so as to get some practice in determining when the purple color has been
replaced by the golden yellow.) Also, as the reaction approaches its endpoint, it is best not
to look at the time on the stopwatch. This will help you to remove any bias due to an
expectation from previous results.

7.

Repeat this procedure for Experiment 1 twice more. All three trials should agree to within
10 seconds.

8.

Now, perform triplicate trials for Experiments #2 and #3 as well.

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Data Analysis
1.

Calculate the Initial Concentration, in units of Molarity, for each reagent used in each of
the three trials in this experiment. Make an appropriate Table of these concentrations.

2.

Calculate the Reaction Rate for each trial using an average of the Time required for the
reaction to go to completion. Add these to your above Table.

3.

Calculate the Reaction Order for each Species; m and n. (See the note for Pre-Lab
Question 2 and follow the same procedure here.) Report two values for each Reaction
Order; the exact experimentally determined value and the nearest Integer value.

4.

Report the Reaction Rate Law.

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Post Lab Questions

1.

Why is it necessary to keep the Total Volume of reagents in each of the four trials in this
experiment the same?

2.

We have labeled all the Oxalic Acid bottles "Poison." What are the toxic effects of
ingesting Oxalic Acid? Write an appropriate chemical equation.

3.

The reaction under study is an Oxidation-Reduction reaction. Assign an Oxidation State to

the Carbon and the Manganese in each relevant species. Identify the Oxidation and the
Reduction.