Chemistry 1310 Lab

Name: Jesse Tanner Ward

Lab Section: B02

Student Number: 7766168

Lab Room: 230

Date of Lab: Oct 30th 2015

Bench: 477

Time: PM

Rotation:

Submission Date: Nov 3rd 2015

Laboratory 4: Kinetics

Purpose
The purpose of the lab is to a) determine the rate law for the reaction of iodide ion with persulfate ion using the
initial rates method and b) determine the rate constant for this reaction at different temperatures, from which
activation energy for the reaction can be estimated.

Results
Analysis
table 1: Part A, Trial 1
-

Part A, Run #

[I ] (mol/L)

[S2O82-] (mol/L)

initial rate (mol/L*s)

k (L/mol*s)

0.0385

0.0385

3.62610^-6

0.002446

0.0385

0.0192

2.00210^-6

0.002708

3
Temperature =296.15K

0.0192

0.0385
2.26910^-6
0.003069
*note: was unable to actually do experiment in Part A
Table 2: Part B Trials
Time (s)
initial rate (mol/L*s)

Part B, Trial #

Temperature (K)

309.65

44

1.09310^-5

0.007375

304.65

81

5.94010^-6

0.004007

294.65

129

3.72810^-6

0.002516

287.15

231

2.08210^-6

0.001405

278.90

426

1.12910^-6

0.000761

4
-

k (L/mol*s)

2-

[I ]=0.0385M, [S2O8 ] = 0.0385M

Calculating the rate law:
Rate = k[I-]a [S2O82-]b
- a

2- b

- a

2- b

Rate2/Rate1= (k[I ] [S2O8 ] / k[I ] [S2O8 ] )

b
(2.00210^-6 /3.62610^-6)= (0.0192/0.0385)
b = 0.853, therefore b is first order, b = 1.
Rate3/Rate1= (k[I -]a [S2O82-]b / k[I -]a [S2O82-]b)
(2.26910^-6 /3.62610^-6)= (0.0192/0.0385)a
a = 0.674, therefore a is first order, a = 1.
Rate = k[I-]1 [S2O82-]1
The orders are expected in the lab to be 0 th, 1st or 2nd order, the decimal values that were found in the calculations
are to be rounded to the closest of these choices. Our closest order is 1 st so the values are rounded to that number.
The overall order of the reaction is 2 after summing the individual reactant orders. This results in k having units
of L/mol*s
Calculating k:
Calculating k can be found through now plugging in our values into the rate law equation above. A sample
calculation is as follows using Run 1 of part A Trial 1.
k = rate /[I -]a [S2O82-]b
k = 3.62610^-6 / [0.0385]*[0.0385]
k = 0.002446 L/mol*s
Average k = (0.002446+0.002708+0.003069)/3 = 0.002741
The average k for Part A Trial 1 is 0.002741 L/mol*s

Graph 1: ln(k) vs. 1/T

0
.0032
-1

.0033

.0033

.0034

.0034

.0035

.0035

.0036

.0036

.0037

-2
ln(k)

-3

f(x) = - 6060.83x + 14.54

R = 0.99

-4
-5
-6
-7
-8
1/T

Calculating Activation Energy & Arrhenius:

ln(k) = -Ea/(RT) +ln(A)
This corresponds to y = mx+b where -EA/R = the Slope m and ln(A) = the intercept b.
R is the ideal gas constant which is equal to 8.3145J/mol*K [1]
b = ln(A)
14.54 = ln(A)
727/50
A=e
L/mol*s
A = 2.063*10^6 L/mol*s
Ea = -R*m
Ea = -(8.3145 J/mol*K)(-6060.83)(mol*K)
Ea = 50.393 KJ
Choosing the allowable mechanisms (all chemicals in equations are aqueous):
M1:
22I I 2 (slow)
- 2
Therefore the Rate = k[I ]
M2:
I - + S2O82- [S2O8*I]3- (slow)
Therefore the Rate = k[I -]1 [S2O82-]1
M3:
32[S2O8*I] + I I2 + 2SO4 (slow)
3- 1
- 1
Therefore the Rate = k[[S2O8*I] ] [I ]
M4:
2I - + S2O82- I2 + 2SO42Therefore the Rate = k[I -]2 [S2O82-]1
The mechanism that would work out of the proposed mechanisms is mechanism 2 as it matches the derived
equation.

Discussion
For this lab there was a big issue that hindered the lab and caused a great lack of confidence in the
results. The Potassium Iodide that was provided was contaminated and unusable for the lab so for Part A of the
lab the data had to be provided by the T.A. This data was for only one trial so the results can not be averaged and
cannot be considered reliable due to having not done the actual experiment in person. With this issue present one
cannot say anything as to the validity of the rate law that was derived. There is simply to much room for error.
Part B was started once some Potassium Iodide was tracked down to use for that portion of the lab and whatever
data is used from that portion in the labs during calculations is likely more accurate. This is assuming that the
new solution had no contamination issues as well.
No recorded data was excluded from the lab in this report however initial trials resulted in instantaneous
reactions and were not recorded in the data sheets. This is due to realizing that the KI was not Potassium Iodide.
The graph results were quite linear in nature with a R 2 factor of 0.99, given this result The Arrhenius and
Activation Energy are both likely quite accurate to the plotted data. There is not much that can be done to
improve this segment of the lab except for using more accurate and precise tools during the lab while eliminating
human error as much as possible.
Of the proposed mechanisms the one that matches the rate law that was derived is the second mechanism. The
activation energy for the reaction then corresponds to the first step of mechanism two. The activation energy for
the second step is not considered in the reaction calculations and is therefore either negligible or the energy
requirement is much less than the energy requirement of the first step in this mechanism. The overall reaction is
defined by the first step and will not proceed unless the requirements of the first step are fulfilled.

Sources of Error
There is likely plenty of error in the lab due to many reasons.
1) The largest source of error is the contaminated KI that was provided, this effectively ruined Part A of the lab.
This causes anything with Part A data to be questionable
2) There will be error in the times that were recorded for the reactions. This is due to a human taking a best guess
as to when to stop the timer and will likely result in longer times than expected.
3) The solutions were giving a short amount of time to reach an equilibrium temperature and may not be
perfectly match.
4) The solutions may not match the ice baths temperature so they may change temperature as the mixing is
occurring.

Conclusion
The lab had a large setback that effectively ruined Part A through no error on the students part. Despite
this the rest of the lab was able to be done. A rate law of Rate = k[I-]1 [S2O82-]1 was determined. k at standard
conditions had an average value of 0.002741 L/mol*s for the Part A trial that was given. Activation Energy was
2
50.393 KJ while the Arrhenius value was 2.063*10^6 L/mol*s and the R factor was 0.99. Mechanism two of
the proposed mechanisms is the one that matched the derived rate law equation.

References
1. Physical Constants of Organic Compounds, in CRC handbook of Chemistry and Physics, 92st ed. (internet
version 2012), Haynes, W.A., Ed.; CRC Press: Boca Raton, FL. http://hbcpnetbase.com/ (accessed Oct 5 2015)