Umar Principe Mohammed

7767461
Section: B04
Rotation: 2
Room #: 206
Locker #: 1377
Experiment 4
Kinetics
Date and time of experiment: March 5th, 2014 at 8:30-11:30 AM
Submitted: March 9, 2015

Purpose
The purpose of this experiment is to utilize the methods of initial rates learned through
lectures and to apply that ability to determine the rate law for the reaction of iodide ion with
persulfate ions. The other purpose is to conduct the same experiment at different temperatures
and determine the rate constant in which the activation energy of this reaction can be estimated.
Analysis
The three kinetic experiments in part A

Experiment 1
Experiment 2
Experiment 3

[I-]
(mol/L)

[S2O82-]
(mol/L)

0.03846
0.03846
0.01923

0.03846
0.01923
0.03846

Initial Rate

(
)
()()
4.22106
1.88 106
2.18 106

k (()())

Temp.
()

0.00285
0.00254
0.00295

22.0
22.0
22.0

The five kinetic experiments at different temperatures in part B

Initial Rate
k (()())

(
)
()()
Experiment 1
0.03846
0.03846
1.36x10-6
0.000919
Experiment 2
0.03846
0.03846
4.04x10-6
0.00273
-7
Experiment 3
0.03846
0.03846
8.81x10
0.000595
Experiment 4
0.03846
0.03846
8.53x10-6
0.00573
-6
Experiment 5
0.03846
0.03846
1.53x10
0.011
Determination of the rate law for the reaction of iodide and persulfate ions.

[I-]
(mol/L)

[S2O82-]
(mol/L)

Rate = k [I-]a [S2O82-] b

Calculation of power of [I-]

[I ] 1
1
=(
)
[I ] 2
3
4.22 106
0.03846
=(
)
2.18 106
0.01923
1.94 = 2
1.94 = 2
1.94
=
2
1

Temp.
()
9.00
21.0
2.0
30.0
40.0

Calculation of power of [S2O82-]

[2 8 2 ] 1
1
=(
)
2
[2 8 2 ] 3
4.22 106
0.03846
=
(
)
1.88 106
0.01923
2.24 = 2
2.24 = 2
2.24
=
2
1

The rate law of this experiment is determined to be

1

= [ ]1 [2 8 2 ]

And is second order in the overall reaction and first order in each individual ion

Calculations for k in experiment 1 table 1

( 1) = [ ]1 [2 8 2 ]1
4.22 106 = ((0.03846)1 (0.03846)1 )
4.22 106 = (1.48 103 )
4.22 106
=
1.48 103
= 0.00285

()()

Calculations for k in experiment 2 table 1

( 2) = [ ]1 [2 8 2 ]1
1.88 106 = ((0.03846)1 (0.01923)1 )
1.88 106 = (7.40 104 )
1.88 106
=
7.40 104
= 0.00254

()()

Calculations for k in experiment 3 table 1

( 3) = [ ]1 [2 8 2 ]1
2.18 106 = ((0.01923)1 (0.03846)1 )
2.18 106 = (7.40 104 )
2.18 106
=
7.40 104
= 0.00295

()()

Calculation of average value for k in table 1

Average k =

(k(experiement 1) + k(experiment 2) + k(experiment 3)

3

Average k =

0.00285 + 0.00254 + 0.00295

3

Average k = 0.00278
Calculations of k for table 2
( 1) = [ ]1[2 8 2 ]1
1.52 106 = ((0.03846)1 (0.03846)1 )
1.52 106 = (1.48 103 )
1.36x106
=
1.48 103
= 0.000919

()()

( 2) = [ ]1[2 8 2 ]1
3.59 106 = ((0.03846)1 (0.03846)1 )
3.59 106 = (1.48 103 )
4.04x106
=
1.48 103
= 0.00273

()()

( 3) = [ ]1[2 8 2 ]1
3.87 106 = ((0.03846)1 (0.03846)1 )
3.87 106 = (1.48 103 )
8.81x107
=
1.48 103
= 0.000595

()()

( 4) = [ ]1[2 8 2 ]1
8.33 106 = ((0.03846)1 (0.03846)1 )
8.33 106 = (1.48 103 )
8.53x106
=
1.48 103
= 0.00573

()()

 ( 5) = [ ]1[2 8 2 ]1
1.14 105 = ((0.03846)1 (0.03846)1 )
1.14 105 = (1.48 103 )
1.53x105
=
1.48 103
= 0.01

()()

ln k vs 1/T
0
0.00315 0.0032 0.00325 0.0033 0.00335 0.0034 0.00345 0.0035 0.00355 0.0036 0.00365 0.0037
-1
-2
y = -6648.7x + 16.691
R = 0.9955

ln k

-3
-4
-5
-6
-7

-8

1/T (K)

Calculation of Activation Energy (Ea):

Utilizing the Formula
=

1
( ) +

Can be related to
y= mbestx + b, where
mbest =

The Ea can be calculated using this formula

-6648.7 = -8.314
1

= 55250 (1000 )
= 55.25

Calculation of the Arrhenius pre-exponential factor A

Using the same two formulas and relating them together
=

1
( ) +

And
= +
Where ln A = b and with the Arrhenius pre-exponential factor A can be solved using this formula
=
= 16.691
= 16.691

= 1.77107 ()()
Expected rate laws of the four proposed mechanisms from page 82 of the chemistry lab book:
Proposed Mechanism
1
2
3
4

Rate Law Equation

= [ ]2
= [ ][2 8 2 ]
= [ ]2 [2 8 2 ]
= [ ]2 [2 8 2 ]

The slow step of Mechanism two is the rate determining step thus the rate law equation is based
off that step, and that step is directly related to the rate law derived using the method of initial
rates of = [ ][2 8 2 ]

Discussion
Utilizing the amount of accuracy and precision used throughout the experiment results in
a very high confidence in the validity of the rate law derived from the experiment of initial rates.
The instruments used to deliver and acquire all the required liquids such as the as the liquid
dispenser for the Sodium Persulfate to deliver exactly 5ml of sodium persulfate and the pipette
used to deliver the 1ml of starch. Utilizing the burettes and pipettes to deliver the other solutions
also aided in the accuracy of this experiment and it was vital that there was exactly the required
amount of the specific solution or else the reaction time could have been affected, affected the
overall rate of the reaction. Through the whole experiment there is very little room for error
when talking about just the instruments used however there is error in consistency of timing the
reactions and to acquire thermal equilibrium throughout the 2nd part of the experiment. It is very
hard to consistently time when the reaction occurs as it depends on the person timing the reaction
as opposed to having an automatic timer. When consistently making sure that thermal
equilibrium is met the test tube had to be repeatedly taken in and out of the water bath to keep
the temperature the same as the one recorded and this may have affected the consistency of the
timing of the reaction.
There was no data excluded from any of the analyses as every experiment remained
consistent with expected results thus resulting in successful trials throughout.
Based on the graph created for this experiment, the accuracy of the activation energy and
the Arrhenius pre exponential factor that was derived is very high. Each of the 5 points are very
close the best fit line resulting in a R2 value of 0.9955 which is very close to 1 resulting into an
almost ideal representation of the best fit line through all of the recorded points. To result in an
even more accurate representation more points could have be used, however through this result 5
points is more than enough to have an accurate best fit line.
The activation energy calculated and determined of = 55.25 from the graph from this
experiment corresponds to the slow step of the mechanism because this step is also the rate
determining because it has the highest activation energy throughout the whole reaction, thus the
reaction cannot undergo unless it goes over this step, this is why the fast step of the reaction has
no effect on the overall reaction because it has a much lower activation energy which is already
surpassed after the slow step has been passed. For example in mechanism #2 the activation
energy would be applied to the rate determining step (slowest step):

This step would contain the highest activation energy throughout the whole reaction and the
outcome of the overall reaction relies on this step to undergo.

Conclusion
In conclusion this experiment resulted in being very successful with very little errors
effecting the final results as the rate law derived through the method of initial rates for the
reaction of iodide and persulphate ions resulted in being
which
matches exactly the purposed rates of mechanism 2 within the lab book. The activation energy
corresponds to the slow step and resulted in being = 55.25 while the Arrhenius pre
exponential factor is 1.77107 ()() . All the required values were able to be derived and determined
thus resulting in a successful experiment.