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Kinetics Lab Report

Comprehensive General Chemistry 3 (University of Chicago)

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Kinetics: "Iodine Clock" Lab Report

Introduction​: In order to describe the chemical kinetics of a reaction, it is desirable to determine

how the rate of reaction varies as the reaction progresses. The rate law is a mathematical
equation that describes the progress of the reaction and has the following general form for the
reaction aA + bB --> cC + dD:

rate ​= -d[A]/(a(dt)) = k[A]​m​[B]​n

[A] and [B] are concentrations of the reactants and k is the rate constant. The variables m , n
and k can only be determined experimentally. In this experiment, the oxidation reaction of
iodide by peroxydisulfate is performed. The rate law for this reaction is as follows:

rate ​= -Δ[S​2​O​8​2-​]/Δt = k[I​-​]​m​[S​2​O​8​2-​]​n

This lab provides an opportunity to understand different concepts of chemical kinetics such as
the reaction rate, rate constant, and reaction order. In this lab-- using several mixtures of the
iodide and peroxydisulfate solutions-- it is possible to calculate the reaction order and the
reaction constant of the chemical reaction. By manipulation of temperature, it is also possible to
understand the temperature dependence of the rate constant as well as determine the activation
energy of the reaction using an Arrhenius plot. Understanding chemical kinetics is important
because of its practical applications. For example, understanding rates of reaction is important
in the manufacturing of ammonia for fertilizer using the Haber process. If the reaction to produce
ammonia is conducted at a low temperature, the rate of reaction will be too slow. Because the
manufacturers want to produce as much fertilizer as possible, they must manipulate the
temperature to produce a satisfactory rate.

Experimental​:​ F
​ or the first portion of this experiment, 5 "Mixtures" are prepared, with varying
concentrations of solutions; the concentrations are summarized in the following table:

Mixture # I​-​ (0.20M) SO​4​2- S​2​O​3​2-​ (0.01M) Starch (drops) H​2​O S​2​O​8​2-​(0.14M)*
(0.33M)

1 50 25 10 10 5 10

2 25 30 10 10 25 10

3 10 33 10 10 37 10

4 10 27 10 10 28 25

5 10 16 10 10 14 50

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All of the solutions amounts are in mL, except starch. Combine all of these solutions, except
S​2​O​8​2-​ into a beaker and bring the Mixture to room temperature in a water bath. Separately heat
S​2​O​8​2-​ in the same bath. Once the Mixture and S​2​O​8​2-​ reach the same temperature, combine the
two while on a magnetic stir plate and begin recording the time on a stopwatch. After stirring for
ten seconds, return the combined Mixture to the bath and stop the stopwatch once the Mixture
reaches a blue color.

For the second portion of this experiment, repeat the above procedure with three volumes of
Mixture 4. Run the same experiment, but in a 10 ℃, 30 ℃, and 40 ℃ bath for trials 1, 2, and 3,
respectively (we don't need to do 20 ℃ because our room temperature trial in the first part of the
experiment serves as our data point).

Record the initial and final temperature for every trial; take note of qualitative observations at
each step and dispose of each solution in the Iodine waste bin.

[No deviations were made from UChicago General Chemistry Lab Manual]

Data Analysis​:

Qualitative

For all mixtures, once the peroxydisulfate was added the solutions turned from clear to blue
after a certain amount of time Δt.

Quantitative

Table 1: Rate of Reaction for Each Mixture

Mixture # T​initial (℃)
​ T​final (℃)
​ Δt (s) -Δ[S​2​O​8​2-​]/Δt (M/s)

1 19.6 19.6 83 6.02E-6

2 19.8 19.3 158 3.16E-6

3 19.9 19.8 398 1.26E-6

4 19.5 19.7 202 2.48E-6

5 19.6 19.8 97 5.15E-6

Sample Calculation; -Δ[S​2​O​8​2-​]/Δt, Mixture 1:

Moles of S​2​O​3​2-​ = 0.10L x .01M = .0001 mol S​2​O​3​2-​ x (1 mol S​2​O​8​2-​/1 mol S​2​O​3​2-​) =
.00005 mol S​2​O​8​2-​/0.10L = .0005M S​2​O​8​2-
.0005M S​2​O​8​2-​/83s = 6.02E-6 M/s

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Table 2: Relationship Between Iodide Concentration and Rate

Mixture # [I​-​] (M) -Δ[S​2​O​8​2-​]/Δt (M/s) log([I​-​]) log(-Δ[S​2​O​8​2-​]/Δt (M/s))

1 0.10 6.02E-6 -1.0 -5.22

2 0.050 3.16E-6 -1.3 -5.50

3 0.020 1.26E-6 -1.7 -5.90

Sample Calculation; [I​-​], Mixture 3:

0.010L x .20M = .002 mol I​-​/.10L = .020M I​-

log(.020M) = -1.7

Figure 1: Relationship Between Iodide Concentration and Rate

Table 3: Relationship Between Peroxydisulfate Concentration and Rate

Mixture # [S​2​O​8​2-​] (M) -Δ[S​2​O​8​2-​]/Δt (M/s) log([S​2​O​8​2-​]) log(-Δ[S​2​O​8​2-​]/Δt) (M/s))

3 0.014 1.26E-6 -1.9 -5.90

4 0.035 2.48E-6 -1.5 -5.61

5 0.070 5.15E-6 -1.2 -5.29

Sample Calculation; [S​2​O​8​2-​], Mixture 4:

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0.25L x 0.14M = 0.0035 mol/0.1L = .035 mol S​2​O​8​2-

log(.035) = -1.5

Figure 2: Relationship Between Peroxydisulfate Concentration and Rate

Table 4: Raw Data for Each Temperature

Target Temperature T​initial (℃)
​ T​final (℃)
​ Δt (s)
(℃)

10 11.0 11.0 253

20 19.5 19.7 202

30 27.1 27.1 105

40 39.0 39.0 43

Table 5: Relationship Between Temperature and Rate

Target T (℃) Average T (℃) Δt (s) -Δ[S​2​O​8​2-​]/Δt (M/s) k(T)

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10.0 11.0 253 1.98E-3 1.63E-3

20.0 19.6 202 2.48E-6 2.04E-6

30.0 27.0 105 4.76E-6 3.92E-6

40.0 39.0 43 8.93E-6 7.35E-6

Sample Calculation; m and k​b​:

log(-Δ[S​2​O​8​2-​]/Δt) = log(k​b​) + m x log([I​-​])
From Figure 1... y = 0.972x - 4.24
m = 0.972
k​b​ = 10​-4.24​ = 5.75E-5

Sample Calculation; n and k​a​:

log(-Δ[S​2​O​8​2-​]/Δt) = log(k​a​) + n x log([S​2​O​8​2-​])
From Figure 2... y = 0.868x - 4.31
n = 0.868
k​a​ = 10​-4.31​ = 4.90E-5

Sample Calculation; k:
k​a​ = k[I​-​]​m
k = (4.9E-5)/(0.020​0.972​)
k = 2.20E-3

k​b​ = k[S​2​O​8​2-​]​n
k = (5.75E-5)/(0.014​0.868​)
k = 2.34E-3

Average k = 2.27E-3

Sample Calculation; k(T), 10.0 ℃:

rate​ = -Δ[S​2​O​8​2-​]/Δt = k[I​-​]​m​[S​2​O​8​2-​]​n
1.98E-6 = k(0.020)​0.972​(0.035)​0.868
k(10 ℃) = 1.63E-3

Table 6: Different Logarithms of Various Rate Constants

T (℃) T (K) 1/T (K​-1​) k(T) log(k) ln(k)

11.0 284.15 3.52E-3 1.63E-3 -2.79 -6.42

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19.6 292.75 3.42E-3 2.04E-3 -2.69 -6.19

27.1 300.25 3.33E-3 3.92E-3 -2.41 -5.54

39.0 312.15 3.20E-3 7.35E-2 -2.13 -4.91

Figure 3: Arrhenius Plot of Table 6

Sample Calculations, Arrhenius Plot:

ln(K) = ln(A) - (E​a​/R)(1/T)
From Figure 3... y = -4999x + 11.1
A = e​11.1​ = 6.62E4
E​a​ = -4999 x -8.314 = 41561 J = 41.56 kJ

Discussion​: In this lab, the rate constant was determined to be .00227 L mol​-1​ s​-1​. In addition, the
order of the reaction were calculated to be m = 0.972 and n = 0.868 and the total order is 1.840.
This results in the overall rate expression: rate = [I​-​]​0.972​[S​2​O​8​2-​]​0.868​. Because the rate constant is
dependent on the temperature, this rate expression is only applicable at room temperature.
Although there aren't perfectly-defined "known values" for the reaction orders, both m and n are
supposed to be ~1. Both our m and n values were relatively close to this value. We 0.868 for our
n value, a 13.2% error; meanwhile, we got 0.972 for our m value, a 3.8% error. The overall rate
of 1.840 deviates from the approximate "known" value of 2 by 8.0%.

Figure 3 illustrates the effect of temperature on the rate constant; as temperature increases, the
rate constant increases for this reaction. Also, by determining the rate of reaction for different

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temperatures for Mixture 4, it was possible to calculate the activation energy. Using the
Arrhenius plot (figure 3) and the equation, ln(K) = ln(A) - (E​a​/R)(1/T), the activation energy was
computed to be 41.6 kJ/mol.

There are several possible sources of error that could affect our rate constant and activation
energy calculations. Determining when the reaction was complete was problematic. It was
uncertain whether the first presence of blue signified the end of the reaction or the presence of
blue throughout the solution signified the end. This discrepancy affects the change in time,
which affects the calculation both the rate constant and the activation energy. We waited until
the entire solution was blue, which could have consistently overestimated our reaction times
and consequently underestimated our rates. Another possible source was the variation of
temperature for each sample. In order to produce accurate rate constants, the temperature must
remain constant for the entire reaction. It is possible to keep the temperature constant by
observing the temperature and adding ice or boiling water to the bath as needed. The presence
of unwanted ions in solutions can also have an affect on calculations. The presence of metal
ions such as copper, even at small concentrations, can catalyze the reaction. In each mixture, a
different concentration of tap water was added with different concentrations of unwanted ions.
This error can be avoided by adding a complexing agent like sulfate and using distilled water,
which is available but unreliable in our lab.

Considering the consequences of the kinetic salt effect, sulfate solution was added to all
mixtures in the experiment. The kinetic salt effect is effect of the salts in solution on the rate of
reaction. When reactions involving ionic compounds occur in solution, the addition of a salt can
speed up, slow down or have no effect on the rate of reaction. Depending on the preexisting
ionic strength of the solution, a certain amount of sulfate solution is added to each mixture to
keep constant the ionic strength for all mixtures. In Mixture 1, the moles of sulfate were 0.025L x
.33M = 0.00825 moles. In mixture 2, 3, 4, and 5 the moles of sulfate were 0.0099, 0.0109,
0.00891, and .00528, respectively.

The bath temperature changes only slightly because of the high specific heat of water. The
equation q = mcΔT illustrates the reasons why it is difficult to effect the temperature significantly.
Because the mass of the bath is large and the specific heat of water is relatively large, the
samples would need a large amount of heat energy to produce a large change in temperature.

Conclusion​: This lab provided an opportunity to experimentally determine the rate constant and
the order of the reaction in which iodide was oxidized by peroxydisulfate reaction. In this lab, the
rate constant was determined to be .00227 L mol​-1​ s​-1 ​and the total order of the reaction was
1.840. The overall rate expression was rate = [I​-​]​0.972​[S​2​O​8​2-​]​0.868​. The "correct' values for the m
and n of this reaction are approximately 1; we got quite close to these values. The effect of
temperature on the rate of constant was also examined in this lab. Plotting these effects
produced an Arrhenius plot that was used to derive the activation energy for the reaction of 41.6
kJ/mol. There were some sources of error like the endpoint of the reaction, the variations in
temperature, and the presence of interfering ions. It was difficult to determine which shade of

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blue signified the end of the reaction. It was also difficult to keep the temperature constant for
the temperature portion of the lab. Having a supply of ice and boiling water could aid in
minimizing variations. The variations of the temperature were not an issue for the room
temperature portion because the bath water had a large mass and the specific heat of water is
relatively large. Finally, the presence of ions like copper could catalyze the reaction. This
unwanted effect could be reduced by using a complexing agent or by using distilled water.
Another source of error was the effect of ionic strength on the rate of reaction. The sulfate was
added to keep the ionic strength equal for all mixtures.

Sources Cited​:
1. Zhao, Meishan and Dragisich, Vera.​ General Chemistry Experiments​. Hayden-McNeil
Macmillan Learning, 2018.

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