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Reaction Kinetics of the Iodination of Acetone

Conference Paper · October 2014

DOI: 10.13140/2.1.4981.7288

0 30,622

3 authors, including:

Savannah Brooke Carroll

University of Tennessee


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Chemistry 479 Experiment 4

Reaction Kinetics of the Iodination of Acetone

Savannah Carroll
Lab Partner: Alexis Hughes
Department of Chemistry
University of Tennessee, Knoxville, TN
November 5, 2014


Reaction kinetics for the iodination of acetone, a color changing reaction, in the presence

of an acid catalyst were studied using spectrophotometer constructed in the lab. These results

were equivalent to what may be recorded using a commercial spectrophotometer. The purpose of

this experiment is to determine if the iodination reaction is a zero, first, or second order reaction.

By systematically varying the concentrations of the reactants, the rate law is determined. The

order of the reaction was also determined by creating an absorbance versus time plot with a

linear fit for the rate law.


The purpose of this experiment is to determine if the iodination of acetone is a first,

second, or third order reaction. The time of the reaction is the time it takes for the brown color of

the iodine to disappear meaning the concentration of iodine has become zero—this is measured

by the spectrophotometer. The rate at which a chemical reaction occurs is dependent of the

nature of the reaction, concentration of the reactants, temperature, and the presence of catalysts

(in this case HCl). In this experiment the kinetics of the reaction between iodine and acetone in

acid solution were studied, and the reaction proceeds as follows:


The rate of this reaction is dependent upon concentration of the hydrogen ion and concentration

of the reactants (Slowinski, Wayne, Masterton 1973). The rate law is therefore: Rate = k

(acetone) m (I2) n (H+) p where m, n, and p are orders of the reaction and k is the rate constant for

the reaction. The rate law is useful in the description of substances that can influence the rate of

the reaction. These influences can be grouped into two categories: those whose concentrations

change with time, and those whose concentrations do not necessarily change with time. These

influences can be changed between experiments to show how they influence the rate of a

reaction (Tinoco 1978).

The order of the reaction, that describes the way the rate of the reaction depends on

concentration, may be determined by plotting absorbance data from each reaction versus time

and utilizing the most linear function. Also from these plots, if the reaction is zero order with

respect to iodine as the literature suggests, one can determine the rate constant from the negative

slop of the graph. Since this experimental data recorded by the spectrophotometer is proportional

to what can be recorded from the commercial instrument, these conclusions can be confirmed.

The rate may also be expressed by the following equation, which says that the change in

concentration of the iodine divided by the time required for that change determines the rate:

Rate= -∆ (I2) / ∆t (Slowinski 1973).

The spectrophotometer is able to measure this change in concentration by the color loss due to

the presence then the loss of iodine. It is important to note that here, iodine is the limiting

reactant in excess of acetone and HCl. Since the constant rate is being varied by the change in

concentrations, we can use the rate of two reactions to solve for the order, this will be discussed

in the “Results” section of this experiment.

A Zero Order Reaction

A zero order reaction has a constant rate, therefore the rate law is rate=k where k has

units of Ms-1, and the sum of the exponents in the rate law is equal to zero. A change in

temperature is the only thing can affect the rate of a zero-order reaction, and if concentration

from a zero order reaction is plotted against time then the result is a straight line with the slope

being the negative of the rate constant, -k.

This experiment utilizes the relationship between concentration of a reactant and time.

The integrated rate law, in which the equation expresses the concentration of a reactant as a

function of time. The integrated rate law of a zero-order reaction is given as:

[A]t = -kt + [A] 0

A First Order Reaction

A first-order reaction has a rate proportional to the concentration of one reactant and can

be expressed as rate=k [A] with units of sec-1. The integrated form of a first order reaction can be

expressed as ln [A]t = -kt + ln [A] 0 or ln [A]t [A] 0 = -kt or [A] = [A] 0 e-kt. A first order reaction

can be determined by plotting a graph of ln [A] vs. time and a straight line with a slope –k should

result (Slowinski 1973).

A Second Order Reaction

A second-order reaction has a rate proportional to the product of the concentrations of

two reactants or to the square of the concentration of one reactant. For example, rate = [A] 2 or

rate =k [A][B] (in other words, the sum of the exponents is two). The integrated rate law of a

second order reaction is:

1 1
= + 𝑘𝑡
[𝐴] [𝐴]0

With the laboratory data, plots produced for [A] versus time, ln [A] versus time, and 1/[A] versus

time, in order to find the function with the linear fit. The iodination of acetone is convenient

because the color of the iodine reactant is readily observable and the change in concentration of

the iodine can be easily monitored by our spectrophotometer and the reaction proceeds quickly

enough for multiple trials but slowly enough to obtain measurements. Also, the reaction is zero-

order with respect to the iodine so the change in concentration is linear with time. This also

allows the initial rate of the reaction to be calculated as an average rate of the change in iodine

concentration over relatively long periods of time.

Experimental Procedure

A spectrophotometer that was built in the previous laboratory was assembled with a blue

diode as a light source for the initial step. LABview software was installed on a PC in order to

record data continuously throughout the reaction. Next, a dilute of iodine was prepared by setting

the voltmeter to read 3.5 Volts with about 4 mL of water, then Iodine was added drop wise until

the voltage was about 1.0 Volts. Next, the commercial spectrophotometer was used to record a

spectrum of the dilute from wavelengths 300nm to 800nm. On the commercial spectrum,

markers were placed at the location of the wavelengths of the blue diode. The blue diode was the

best choice because its wavelength is about 470nm, and the commercial iodine spectrum is

expected to produce highest absorbance at these wavelengths. Four trials were taken to obtain

data, and throughout these trials the volume of the mixture of iodine, acetone, HCl, and water

was 3.5 mL for each trial and the amount of each reactant was varied. A table of the

concentrations during each trial is shown below.

Table 1: Reactant Concentrations

Trial 1 Trial 2 Trial 3 Trial 4
Iodine 1.0 1.5 1.0 1.5
Acetone 1.0 0.5 1.5 0.5
HCl 1.0 0.5 0.5 1.0
H2 0 0.5 1.0 0.5 0.5
Total Volume 3.5 3.5 3.5 3.5

The reaction in this experiment can proceed very quickly. For this reason, a pipette was

used to transfer each reactant into a small beaker before each trial so that they could be combined

in the test tube and inserted into the spectrophotometer as quickly as possible. Multiple trials

were taken for each concentration combination. The Beer-Lambert law employed in the last
laboratory (A= -log (𝐼 )) was used a second time to express the data in terms of absorbance.

Results and Discussion

Figure 1: Absorbance vs Wavelength Iodine

1.6 Blue: 470 nm Yellow: 595 nm

300 400 500 600 700 800
Wavelength (nm)

The commercial spectrum suggests iodine will have the highest absorption at

wavelengths from about 540-580 nm. This wavelength range is closest to the wavelength omitted

by the yellow diode, suggesting this would have been a better choice. However, the dilution used

in the commercial spectrum was modified following some test reactions. In the future, another

commercial spectrum should be produced for the second dilution because the use of the blue

diode gave desirable results for the purpose of this experiment.

As mentioned in the introduction, a reaction is a zero order if when the concentration is

plotted versus the time the result is a straight line representing a constant rate. Therefore, the

iodination of acetone is a zero order reaction and this is demonstrated in experimental plots for

all concentration as well as the commercial spectrum. The slope of this line is the negative of the

rate law constant (-k). The slope and therefore the rate law constant for each reaction as well as

the commercial spectrum are shown in Table 1. Table 2 shows the orders of the reactants

calculated using the equation: Rate x/Rate y = (k [acetone]a[iodine]I[HCl]h)x ÷ (k

[acetone]a[iodine]I[HCl]h)y, an example is shown in Sample Calculation IV. Solving for a

resulted in a value of 0.69, which rounds to one. Solving for h resulted in a value of 0.71 which

also rounds to one. Adding the three exponents result in a pseudo-order of two.

Table 2. Rate Law Constants (k)

Trial 1 Trial 2 Trial 3 Trial 4 Average
k (1/Ms) 0.0011 0.0008 0.0017 0.0018 0.00135

Data from individual plots of absorbance versus time was extrapolated to plot absorbance

versus time for each reaction on one graph for the start and finish of each. The combined data is

shown below, and an example plot can be found in the appendix that shows the absorbance

before the start of the reaction as well as stabilization after the concentration of iodine reached

zero. As can be seen in Figure 2, a linear function with a negative slope resulted from each

reaction all of which varied in concentration of the reactants. Therefore, the reaction can be

considered zero order with respect to iodine from this visual representation. It can also be said

from this data that each reaction lasted between 100-120 seconds. Table 1 shows the rate

constant from each reaction taken from the negative of the slope; these values indicate the rate is

constant. Mathematically, the reaction is determined to be zero order with respect to iodine by

finding the rates of two reactions, the corrected concentrations of iodine, and solving for the

coefficient; this is shown in Appendix A. Sample calculations.

In “Reaction 2” acetone and HCl were not present in excess. For this reason, the reaction

took about 180 seconds longer and values for k and the rate was not useful for this experiment.

In the reactions where acetone and HCl are in excess, their concentrations remain mostly

constant throughout the reaction.

Figure 2: Absorbance Vs. Time







0 20 40 60 80 100 120
Time (s)

Reaction 1 Reaction 2 Reaction 3 Reaction 4

Figure 3 shows the natural log of the absorbance for each of the four reaction versus

time. The non-linearity of the graph further confirms that the reaction is zero order with respect

to iodine. If the reaction were first order, there would be a linear trend for this plot.

Figure 3: ln(Absorbance) Vs. Time

ln(A) 4

0 20 40 60 80 100
Time (s)

ln(A): T1 ln(A): T2 ln(A):T3 ln(A): T4

A plot of the inverse of the absorbance versus time also failed to show a linear trend. This

plot, Figure 4, represents what would be a second order reaction if the trend wasn’t exponential.

This graph tells us that during the timed reaction the inverse of the absorbance increases

exponentially therefore the absorbance must be decreasing.

Figure 4: 1/Absorbance Vs. Time


0 20 40 60 80 100 120 140
Time (s)

1/a: T1 1/A: T3 1/A: T4


A potentially significant source of error in this experiment is room temperature. As

mentioned in the introduction, temperature is known to affect the rate of the reaction. Since this

experiment occurred over multiple laboratory periods, the room temperature and temperature of

the solutions were likely different each time. In addition to temperature consistency, it would be

beneficial to run more trials and utilize the concentration ratio that produces accurate and precise

results. Other sources of error to be consider include the spectrometer’s voltage readings which

may cause noise in the recorded data.


This reaction is experimentally beneficial for two reasons. First, the color of the iodine

allows the concentration change to be readily followed; second, the reaction turns out to be zero

order. Therefore, the rate of the reaction is independent of the iodine and the rate can be studied

by making the iodine the limiting reactant in an excess of acetone and HCl. The experimental

data supports these conclusions by showing a linear trend for an absorbance versus time plot as

shown in Figure 2, and also by producing similar results for each reaction with varied

concentrations of each reactant. The deductions from these graphical representations of the

reactions can be verified by the kinetics equations. Through these methods, the overall order of

the reaction was found to be zero, and the orders of acetone, HCl, and iodine were found to be

one, one, and zero. Acetone and HCl may be omitted to give the rate law, rate = k [I2]I or rate =

k. The average value for the rate constant which was found for each trial was found to be

0.00135 1/Ms.


A. Sample Calculations

I) Calculation of the corrected concentration (Acetone, Trial 4 shown)


Where M1 is the molarity of the given substance, V1 is the volume used of that

substance, M2 and V2 are the total volume and molarity used

0.5 mL (V1) of a 6 M acetone solution (M1). M2 is the variable in question and V2 is

3.5 mL (total volume used)

M2= [(6M)*(0.5mL)] / 3.5mL

II) Calculation of The Rate (Trial 4)

Using the equation: Rate= [I2]/s x 105

The concentration of Iodine in the sample (0.05 M) and the time it took for the

reaction to go to completion (t = 116s)

Rate= [(0.05)/(120)] = 0.00041

III) Determination of the Order

Rate 4/Rate 3 = (k [acetone]a[iodine]I[HCl]h)2 ÷ (k [acetone]a[iodine]I[HCl]h)3

Where Rate 2 = 1.84729E-5 and Rate 4 = 1.23153E-5 and

[Iodine]2= 0.002142857 and [Iodine]3= 0.001428571

(1.84729E-5) ÷ (1.23153E-5) = [0.0021] I / [0.0014] I

1.50= 1.4997I

I= log (1.5) / log (1.4997)


B. Experimental Data

I) Corrected Concentrations of Reactants and Reaction time

Corrected Concentrations
T1 (M1) T2 (M1) T3 (M1) T4 (M1)
Iodine 0.001429 0.002143 0.001429 0.002143
Acetone 1.714286 0.857143 2.571429 0.857143
HCl 0.285714 0.142857 0.142857 0.285714
Time (s) 116 280 103 116

II) Rates of the Reactions

Rates (M/s)
Rate T1 Rate T2 Rate T3 Rate T4 Average(M/s)
1.23153E-05 7.65306E-06 1.387E-05 1.8473E-05 9.9989E-06

III) Intensity vs Time: Trial 4

Intensity Vs. Time: Trial 4



Intensity (V)



0 20 40 60 80 100 120 140 160
Time (s)

IV) Absorbance vs Time: Trial 4

Absorbance vs. Time: Trial 4
Absorbance 0.3
0 50 100 150 200

V) Absorbance vs Time: Trial 2

Absorbance vs Time: Trial 2








0 50 100 150 200 250 300 350
Time (s)


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III. Meyer, Earl N., and Flourence F. Lask. "Rate and Activation Energy of the Iodination

of Acetone." Journal of the Chemical Society (2010): 1-5.Minnesota State University

Moorhead. Web. 2 Nov. 2014.

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Rate of Chemical Reactions." Chemical Principles in the Laboratory. Philadelphia:

Saunders, 1973. 149, 150-52. Print.

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Print. Fifth.


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