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Experiment 15: Chemical Kinetics

This experiment determines the rate law and rate constant for the reaction between potassium permanganate and oxalic acid by varying their concentrations and measuring reaction rates. Reaction rates are measured at different temperatures to examine the effect of temperature. Rate laws, orders, and rate constants are calculated from experimental data to characterize the reaction kinetics.

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129 views

Experiment 15: Chemical Kinetics

This experiment determines the rate law and rate constant for the reaction between potassium permanganate and oxalic acid by varying their concentrations and measuring reaction rates. Reaction rates are measured at different temperatures to examine the effect of temperature. Rate laws, orders, and rate constants are calculated from experimental data to characterize the reaction kinetics.

Uploaded by

Lutendo Assurance Madzivhaa
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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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.

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