Experiment 15

Chemical Kinetics
 Purpose
• The purpose of this experiment is to
determine the rate of a chemical
reaction (potassium permanganate,
KMnO4, + oxalic acid, H2C2O4) as the
concentrations are varied and to
determine the rate law for the reaction.
 Introduction
• For a reaction
aA+bBcC+dD
1 [A] 1 [B]
rate  ( )  ( )
a t b t

1 [C] 1 [D]
rate  ( ) ( )
c t d t
 Conc/time curve

0.8

0.6
[A], M

0.4

0.2

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

time (arbitrary)
 Different Rates

• Average (this experiment)

• Initial (Experiment 17)

• Instantaneous
 Rate Law
• Rate law---a relationship between
concentrations and rate. For a reaction
aA + bB  products

the rate law often takes the form

Rate = k[A]x[B]y
 Rate = k[A]x[B]y
• [A],[B]: molarities of A and B in
solution
• x, y: orders with respect to A and B,
respectively. (These orders might not
correspond to coefficients from the
balanced equation!)
• k: rate constant
 What We’re Running
• 2 MnO4- + 5 H2C2O4 + 6 H+ 
2 Mn2+ + 10 CO2 + 8 H2O

• We assume a rate law

Rate = k [MnO4-]m[H2C2O4]n

• The rate law and rate constant are not

affected by concentration.
 Strategy
• One pair of experiments (assignments
1 and 2): [MnO4-] is constant and
[H2C2O4] doubles.
• In another pair (1 and 3), [MnO4-]
doubles and [H2C2O4] is constant.

• For each of these pairs, divide the rate

measured in one experiment by that
from another.
• Comparing assignments 1 and 2:
rate 2 [H2C2O4]2 n
( )
rate 1 [H2C2O4]1

• This can be rewritten as

rate 2 [H2C2O4]2
log( )  n log( )
rate1 [H2C2O4]1

• Since rates and concentrations are

known, n (the order with respect to
oxalic acid) is available.
• Similarly, comparing assignments 1 and
3 gives
m
rate 3 [MnO -4 ]3
( )
rate 1 [MnO -4 ]1

• And, therefore,

rate 3 [MnO -4 ]3
log( )  m log( -
)
rate 1 [MnO 4 ]1

From this, m (the order with respect to

MnO4-) is available.
• Once the orders are known, we can
calculate the rate constant from the rate
law.

• Since rates depend on temperature.

we will also look at the effect of
temperature on the rate of this reaction.
 Safety
• Aprons and glasses.

• KMnO4 is a strong oxidant (and also

stains skin and clothing); oxalic acid is
poisonous.

• Waste into waste bottles.

 Safety 2
• If you use the Bunsen burner for heating
water, keep hair, clothing, paper, and
other flammable material away.

• Shut off burner before mixing high-

temperature samples.
 Procedure
• Work in pairs.

• Check out pipettes and bulbs from

stockroom.
• Needed equipment: medium-sized test
tubes; 250- and 400-mL beakers. May
also need ring stand, ring, wire gauze,
and Bunsen burner.
 Quantities of Reactants Used
(P. 15-6) Assignment numbers
#1 #2 #3

Oxalic Acid, 5.0 10.0 5.0

mL
KMnO4, mL 1.0 1.0 2.0
Water, mL 6.0 1.0 5.0
• Mark an X on a piece of white paper.

• Get 75 mL oxalic acid and 15 mL

KMnO4 solutions; record
concentrations.
• Two tubes for each assignment; pipet
desired volumes of oxalic acid and
water into each tube. For use of
volumetric pipets, review Expt. 11 from
CHEM 1031.
• Prepare four additional tubes for
Assignment #1; also pipet 1.0 mL of
KMnO4 solution into each of four small
test tubes. Save these for temperature
study---last part of experiment.

• Start with first oxalic acid-water tube for

Assignment 1. Place the paper behind
the test tube.
• Pipet KMnO4 solution into tube; begin
timing when half the solution has been
added.
• When you can see the X through the
test tube, record elapsed time on your
data sheet.

• Repeat the run you have just

completed; then do duplicate runs for
the other two assignments.
• Effect of temperature: Place two oxalic
acid tubes and two KMnO4 tubes into a
beaker containing warm water (10oC
above room temperature). (If tap water
is not sufficiently warm, use Bunsen
burner.)

• After tubes have been in warm water for

5 minutes or so, add KMnO4 to an
oxalic acid-water mix; record elapsed
time for X to become visible. Repeat.
• Make cool water bath (ice in water) to
get 10oC below room temperature.

• Cool other two oxalic acid-water mixes

and KMnO4 samples. Again mix,
record elapsed time as before. Repeat.
 Calculations
• Concentrations of oxalic acid and KMnO4
from dilution formula:

 Vi 
Mf  Mi  
 Vf 

• Example: 5.00 mL of 0.755 M oxalic acid

diluted to 12.00 mL gives 0.315 M.
• For each assignment, average the times
for the two runs.

 [MnO4-] = [MnO4-]f – [MnO4-]i = -[MnO4-]i

1 [MnO 4 ]
Rate  ( )( )
2 time
•From measured rates, determine orders:

rate 2 [H2C2O4]2
log( )  n log( )
rate1 [H2C2O4]1

rate 3 [MnO -4 ]3
log( )  m log( -
)
rate 1 [MnO 4 ]1

•Round the orders to the nearest integers.

• Go back to the rate law:

Rate = k [MnO4-]m[H2C2O4]n

• You now know rates, concentrations,

and orders. Calculate k for each
assignment and average.
The effect of temperature

• Rate is proportional to
Concentration/time

• ---if the time decreases by a factor of 3

(say), the rate correspondingly
increases by a factor of 3.