Experiment 2: Kinetics of the Reaction Between Permanganate

and Oxalic Acid

Introduction

Chemical kinetics is the branch of chemistry that studies the rate of the reaction, the factors affecting the
rate of reaction, and the mechanism by which the reaction occurs.

Consider the hypothetical reaction:

aA + bB  cC + dD

The rate of the reaction, r can be expressed either as the change in the concentration of a reactant or
product per unit time.

1 𝑑[𝐴] 1 𝑑[𝐵] 1 𝑑[𝐶] 1 𝑑[𝐷]

𝑟=− =− = =
𝑎 𝑑𝑡 𝑏 𝑑𝑡 𝑐 𝑑𝑡 𝑑 𝑑𝑡

Notice that a negative sign is affixed to the expressions involving a reactant because the rate of reaction
is always expressed as a positive quantity. The need for the negative sign is due to the fact that
d[reactant] is always negative.

The rate of a reaction is affected by four (4) major factors: 1) concentration of the reactants, 2)
temperature, 3) presence of a catalyst, and 4) nature of the reactants.

Concentration of the Reactants

The effect of concentration to the rate of the reaction is mathematically shown by its rate law. The rate
law is experimentally determined. For the hypothetical reaction above, the arbitrary rate law is

Rate = k[A]x[B]y

Where k is the rate constant, [A] and [B] are the concentration of reactants A and B, and x and y are
the orders of reaction with respect to each reactant.

The rate orders can be determined by using either the 1) initial rates method or 2) integrated rate laws.

In general, an increase in the concentration of the reactants increases the rate of the reaction.

Reaction Temperature

The effect of temperature to the rate of the reaction is mathematically shown by the Arrhenius equation.

k = Ae-(Ea/RT)
ln k = ln A – (Ea/R)(1/T)

Where k is the rate constant, A is the Arrhenius constant, E a is the activation energy, R is the gas constant
(8.314 J/molK), and T is the temperature in Kelvin.

The equation shows the temperature-dependence of the rate constant, which has a direct effect on the
rate of the reaction.

As a rule of thumb, every 10 oC rise in the temperature of the reaction (temperature range of 20 – 90 oC),
the rate of the reaction multiplies by 2n, where n = ΔT/10.

In this experiment, you will study the kinetics of the reaction between permanganate ion and oxalic acid.
Experiment 2: Kinetics of the Reaction Between Permanganate
and Oxalic Acid
MnO4-(aq) + 5 H2C2O4(aq)  [Mn(C2O4)3]3-(aq) + 4 CO2(g) + 4 H2O(l) + 2 H+(aq)

MnO4- is a purple-colored ion whereas the complex ion [Mn(C2O4)3]3- is golden brown/red wine-colored.
The rate of the reaction can be determined by measuring the time it takes to decolorize MnO4-.

Using initial rates method, you will determine the rate law for the permanganate-oxalic acid system. Using
Arrhenius equation, you will determine the activation energy of the reaction.

Reagents and Materials

0.10 M KMnO4 Hot plate

1.00 M H2C2O4 Ice cubes
50-mL beakers Thermometers
5-mL measuring pipettes Timer

Procedure
Part I: Determination of Rate Law for the Permanganate-Oxalic Acid System

1. Measure the temperature of water.

2. Refer to the table below for the runs to be performed.

Run V 1.00 M H2C2O4, mL V 0.10 M KMnO4, mL V water, mL

1 1.00 1.00 3.00
2 2.00 1.00 2.00
3 3.00 1.00 2.00
4 3.00 2.00 3.00

3. For run 1, mix the required volume of H2C2O4 and water in a 50-mL beaker. Label this as Solution A.
4. In another 50-mL beaker, place the required volume of KMnO4. Label this as Solution B.
5. Add Solution A to Solution B. Start timing as soon as Solution A touches Solution B.
6. Record the time elapsed for the color of the solution to change from purple/violet to golden
brown/red wine.
7. Repeat procedures 3 to 6 for Run 2.
8. For run 3, mix the required volume of KMnO4 and water in a 50-mL beaker. Label this as solution C.
9. In another 50-mL beaker, place the required volume of H2C2O4. Label this as Solution D.
10. Add Solution D to Solution C. Start timing as soon as Solution D touches Solution C.
11. Record the time elapsed for the color of the solution to change from purple/violet to golden
brown/red wine.
12. Repeat procedures 8 to 11 for Run 4.

Part II: Determination of Activation Energy for the Permanganate-Oxalic Acid System

1. Prepare a cold water bath (temperature should be less than the temperature in part I). Record the
temperature of the cold water bath.
2. Prepare Solution A and Solution B of Run 2 from part I.
3. Place Solution A and Solution B in the cold water bath.
4. Wait for 2 minutes before adding Solution A to Solution B. Start timing as soon as Solution A touches
Solution B.
5. Record the time elapsed for the color of the solution to change from purple/violet to golden
brown/red wine.
6. Repeat procedures 1 – 5 but this time use a hot water bath (not necessarily boiling).
Experiment 2: Kinetics of the Reaction Between Permanganate
and Oxalic Acid
Waste Disposal

Dispose of solutions into the designated waste beaker.

Calculations

Determination of Rate Law

1. Using the dilution equation, calculate the initial concentration of MnO4- and H2C2O4 for each run.
2. Calculate the change in [MnO4-] for each run.
3. Use the values from #2 to determine the rate of the reaction (in M/s) for each run.
4. Apply method of initial rates to determine the rate order with respect to each reactant.
5. Calculate the rate constant for each run and get the average rate constant for the reaction at
ambient temperature.

Determination of the Activation Energy

1. Calculate the rate of your reaction for the run at low and high temperature.
2. Calculate the rate constant for the reaction performed at low and high temperature.
3. Make an Arrhenius plot (ln k vs 1/T) using the rate constants you obtained at ambient, low, and high
temperature.
4. Calculate the activation energy and Arrhenius constant of the reaction from the Arrhenius plot.

Points of Discussion

1. Explain how the reaction rate was determined in the experiment. Show equations used to determine
the rate of the reaction.
2. Explain the significance of the rate law obtained.
3. Explain how the Arrhenius plot is obtained.
4. Explain the observed trend in rate constant as the reaction temperature is increased.
5. Explain the significance of the activation and the Arrhenius constant obtained in the experiment.
Experiment 2: Kinetics of the Reaction Between Permanganate
and Oxalic Acid
Name: ________________________________________________ Date Performed: ___________________

Co-workers: _________________________________________

_________________________________________

Data Sheet

Part I

Temperature: ______________

Run Total Volume, mL Initial [MnO4-], M Initial [H2C2O4], M Reaction time, s Reaction rate, M/s
1

Reaction order with respect to MnO4-: ______________

Reaction order with respect to H2C2O4: _____________

Rate law: ____________________________

Part II

Initial [MnO4-]: _________________

Temperature, K Reaction time, s Rate of reaction, M/s Rate constant

Equation of the Arrhenius plot: _______________________________

Linearity coefficient, r2: ______________________

Activation energy, Ea (in kJ/mol): _______________________

Arrhenius constant: _________________________