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Introduction
Understanding what factors affect the rate of a chemical reaction, and understanding more about the
process through which a reaction occurs, is a major challenge of chemistry. Determining the rate law for a reaction
can provide information about what factors affect the rate of a reaction and can allow chemists to design reaction
conditions that favor product formation. Knowledge of the rate law of a reaction also provides a first step towards
understanding the process, or mechanism, by which a reaction occurs. Knowing the mechanism of a reaction can
allow us to gain a more detailed theoretical understanding of how and why chemical reactions occur.
In this lab, we will use the spectrophotometer to study the rate of a particular reaction under various
conditions. With this simple but accurate instrument, we will be able to collect kinetic data that will allow for a
determination of the rate law of a reaction. Finally, we will use this experimentally-determined rate law to decide
whether a proposed mechanism for the reaction is plausible and consistent with the experimental data or not.
Safety
Safety glasses or safety goggles and lab coats must be worn at all times in the laboratory.
Gloves must be worn while performing experiments or working with chemicals.
Use caution when inserting glass pipets into the pipet plungers so you do not break the glass pipet.
Discussion
The particular reaction we will study is the iodination of cyclohexanone, C6H10O, to form
2-iodocyclohexanone, C6H9IO:
O O
H H H I
C C
H C C H H C C H
I3 + + H+ + 2I
H C C H H C C H
C C
H H H H
H H H H
As this reaction proceeds, the concentrations of the reactants will decrease as the concentrations of the
products increase. Although it is possible to follow the reaction by measuring any of the reactant or product
concentrations as a function of time, we can simplify things by choosing the most convenient measurement. In this
case, it is easiest to follow the reaction by observing the loss of color in the reaction mixture as the I3 reacts and
disappears, since the I3 ion is reddish-orange and all the other reactants and products are colorless.
To obtain accurate data, we will need a quantitative way to measure these color changes. An instrument
called a spectrophotometer allows us to measure the absorbance of visual light; the I3 ion absorbs some colors of
visible light, allowing only red and orange light to pass through. Furthermore, as the concentration of I3
decreases, the amount of light absorbed will decrease as well (a short review of Beers Law, A = cL, is included
at the end of this Discussion). Thus we will be able to measure the change in concentration of I3 as a function of
time by measuring the change in light absorbance with the spectrophotometer.
Experiment 9 1
Introduction to Reaction Rates
Since we will measure the concentration of I3 as a function of time, we can express the rate of our
reaction as the change in the I3 concentration over the change in time:
[I 3 ]
rate =
t
Since reaction rates are defined as positive quantities and the change in concentration of I3 is a negative quantity
(because it is disappearing), we have to put a negative sign before the ratio.
Note: To be precise, we should use derivatives to define the rate. However, we can avoid the use of
calculus in this case because of our choice of reaction and our method of studying it.
As you learned in lecture, the rate of a reaction depends on the concentrations of the species present in the
reaction mixture. For example, the reaction of I3 with cyclohexanone is quite slow, but adding a few drops of
strong acid speeds the reaction considerably. This observation leads us to assume that the rate of our reaction
depends on the concentration of H+, even though H+ does not appear as a reactant in the stoichiometry of the
reaction. It does appear as a product of the reaction, which has interesting consequences for the reaction carried
out without added acid.
An equation expressing how the rate depends on the concentrations of species in the reaction mixture is
called the rate law for the reaction. We need to know the rate law for our reaction, because it will help to prove (or
disprove) our proposed mechanism. As a general expression of the form of the rate law, we can write:
[I 3 ]
= k[H + ] a [cyclohexanone]b [I 3 ]c
rate =
t
where the orders (exponents a, b, and c) with respect to [H+], [cyclohexanone], and [I3] must be determined by
experiment. The constant k is the rate constant for the reaction.
One piece of information that will make your task easier is that previous experiments have demonstrated
that our reaction is zero order with respect to [I3]. This can be mathematically stated by setting c = 0 in the above
rate law.
We will use this information and simplify the interpretation of our data by using a technique called
flooding. We will carry out the reaction with initial concentrations of cyclohexanone and acid that are very large
compared to the initial concentration of I3 (in other words, we flood the reaction with cyclohexanone and acid)
so that the cyclohexanone and acid concentrations remain approximately constant during the reaction.
Experiment 9 2
Under these conditions, the rate of disappearance of I3 will be constant. Thus we can measure the rate by
considering only the beginning and end points in the reaction. At the beginning of the reaction at time t = 0, there
will be a certain initial concentration of I3, which we can notate as [I3]i. At the end of the reaction, all the I3 will
have been consumed, and the reaction will have reached a final time tf. Since the notation means
final - initial, the rate for this particular experiment can be determined:
0 [I3 ]i [I3 ]i
rate = =
tf 0 tf
Thus the rate of the reaction can be determined simply by knowing the initial concentration of I3 along with the
time at which the reaction is complete. Putting this together with the fact that the reaction is zero order with
respect to I3 (hence c = 0) gives:
[I3 ]i
rate = = k[H + ]ia [cylcohexanone]bi
tf
where the subscripts indicate initial concentrations. You will determine k, a and b.
We will be using a spectrophotometer to track the concentration of the I3 ion as a function of time.
Because I3 is red-orange, it absorbs some colors of visible light, and allows only red and orange light to pass
through. The total amount of light absorbed by a sample of I3 depends on the number of ions in the light path.
More light will be absorbed if the solution is more concentrated, and more light will be absorbed if the sample is
thicker. This reasoning leads to Beers Law, which relates the absorbance A of a molecule at a wavelength to its
concentration c and the length L of the light path through the solution:
A= cL
The proportionality constant is the molar extinction coefficient, which is a constant for a given substance at a
given wavelength. I3 has a wavelength of maximum absorbance of 566 nm, so all of our data in this lab will be
collected at 566 nm. At 566 nm and using identical cuvettes, and L will be constant, so absorbance will be
directly proportional to concentration.
In this experiment, we will know the initial concentration of I3 based on the volumes of initial solutions
we mix together (you will determine this initial concentrations of I3 as part of your Prelab). And we know, based
on Beers Law, that when the absorbance reaches zero, the concentration of I3 must also be zero, so it is at this
point that all of the I3 has been consumed, and the reaction is complete. Because of the specific reaction
conditions we have established (i.e. flooding the reaction with cyclohexanone and acid) we know that the rate of
the reaction will remain constant. We can thus calculate the rate of the reaction simply based on the change in [I3]
and the change in time, with the final [I3] = 0 at the end of the reaction when absorbance is zero. Thus, although
we will be relying on the concept derived from Beers Law that absorbance is directly proportional to
concentration, we will not need to perform any specific calculations using Beers law.
Experiment 9 3
(This Page Intentionally Left Blank)
Experiment 9 4
TF: __________________ Name: __________________________
Grading:
Prelab: _____ / 10
Lab Report: _____ / 20
Safety: _____ / 3
Cleanup: _____ / 2
Total: _____ / 35
(Postlab is worth an additional 10 points)
Experiment 9 5
TF: __________________ Name: __________________________
Quantitative Measurements
Using the Vernier Spectrometer and LoggerPro
For this lab we will be using the Vernier spectrometers to take quantitative measurements of the
absorbance of the reddish-orange I3 ion. The Vernier Spectrometers are the small black boxes connected to the
computers at your lab bench. Using these spectrometers with the computers will streamline data collection.
The Vernier Spectrometer has a small square opening where you can insert the sample cuvette. Only use
the square plastic cuvettes in the Vernier Spectrometers. Never attempt to insert a glass test tube into the
Vernier Spectrometer. In addition, please be careful not to spill any solutions onto the computers or the
spectrometers. All wet work including preparation and mixing of solutions should be done on the lab benches
across the sink from the computers.
If your computer is not already logged in, login to the computer by clicking on Physical Sciences and
entering the password ps1.
On the menu bar at the top of the screen, click on Go ! Applications! LoggerPro 3 and open
LoggerPro. You should see a plot of absorbance versus wavelength appear with a spectrum of colors.
The square plastic cuvettes have a clear side where the light will pass through, and a shaded partially opaque
side. Only handle the cuvettes on the opaque sides. Fingerprints on the clear sides will interfere with your
measurements.
Do not overfill the cuvettes. In this lab you will be filling the cuvettes with exactly 3.0 mL of solution. If you
have measured the volumes carefully, this will fill the cuvettes approximately as full as they should be filled
without overflowing. If you are using cuvette caps, you should be able to place a cap on the cuvette without
spilling any solution. If you overfill a cuvette or spill any solution on the side of a cuvette, pour a little out into
the Used Chemicals beaker and wipe off the outside of the cuvette with a paper towel before proceeding. Be
careful not to get any solution inside the spectrometer equipment.
When inserting the plastic cuvettes into the spectrometer, make sure that the light beam is passing through the
clear sides of the plastic cuvette, not through the cloudy opaque sides. You can do this by looking for the light
beam and observing the cuvette closely, or by lining up the arrow on the upper edge of the cuvette with the
blue dot on the spectrometer.
The cuvette should be inserted firmly into the spectrometer. Less than 1 cm of the cuvette should stick out of
the top of the spectrometer, and the cuvette should not be able to move back and forth much within the
spectrometer. If you are having trouble inserting the cuvette all the way into the spectrometer, ask your TF for
assistance.
Experiment 9 6
TF: __________________ Name: __________________________
Experiment 9 7
TF: __________________ Name: __________________________
4
Collecting Absorbance Data. 5
20
Experiment 9 8
TF: __________________ Name: __________________________
Repeat the entire measurement procedure for Which mixture is this? (circle)
the reaction mixture in the other cuvette (either B or
A B C D
D). Again, continue until 20 minutes has elapsed, or
until the absorbance reaches zero.
Absorbance data:
Time (min) Absorbance
10
11
12
13
14
15
16
17
18
19
20
Experiment 9 9
TF: __________________ Name: __________________________
Lab Report
1. Plot the absorbance as a function of time for your first reaction mixture.
Which mixture is this? (circle)
A B C D
0.4
0.3
Absorbance
0.2
0.1
0
0 5 10 15 20 25 30
Time (min)
2. You should be able to draw a straight line through your data. (You may have to ignore some initial curvature in
the line.) Find the time at which the best-fit line crosses the x-axis; this is the time of completion of the reaction (tf).
tf =
3. Calculate the rate for this reaction mixture using the relationship:
[I3 ]i
rate =
tf
rate =
Experiment 9 10
TF: __________________ Name: __________________________
4. Plot the absorbance as a function of time for your second reaction mixture.
Which mixture is this? (circle)
A B C D
0.4
0.3
Absorbance
0.2
0.1
0
0 5 10 15 20 25 30
Time (min)
5. Draw a straight line through your data. Find the time at which the best-fit line crosses the x-axis; this is the
time of completion of the reaction (tf).
tf =
6. Calculate the rate for this reaction mixture using the relationship:
[I3 ]i
rate =
tf
rate =
7. Your TF will have set up a data table on the blackboard for all groups in your section to enter their
experimentally-determined rates. Record the rates for both of your reaction mixtures on the blackboard under the
appropriate columns.
Experiment 9 11
TF: __________________ Name: __________________________
8. Once all of the class data has been recorded on the blackboard, help to calculate the average reaction rate for
each of the four mixtures. As a group, your section should write those average rates on the board.
9. Fill in the table using the average rate data from your section:
10. Using the above data, determine the order with respect to H+.
Rate Law =
(Copy this rate law into the box for problem 1 on the
Postlab on page 15 of this lab report.)
Rate constant k :
Experiment 9 12
TF: __________________ Name: __________________________
Prelab
This page must be completed before you arrive at the laboratory.
Hand it in to your TF as you enter the lab.
1. In this lab, stock solutions will be available which are 0.23 M cyclohexanone, 0.5 M H+, and 0.018 M I3.
You will combine the following mixtures:
For measuring the order with respect to acid: For measuring the order with respect to cyclohexanone:
+
Mixture A: 0.5 mL H (acid) Mixture C: 0.5 mL H+ (acid)
1.5 mL cyclohexanone 1.0 mL cyclohexanone
0.5 mL distilled water 1.0 mL distilled water
You will then add 0.5 mL of I3 solution to each of these mixtures to start the reaction. The total volume of each
mixture after the I3 is added will be 3.0 mL. Using this information, determine the initial concentrations of H+,
cyclohexanone, and I3 at the start of the reaction for each of these mixtures. Fill in the initial concentrations in
the chart below, and copy this data into the similar chart on page 7 of the laboratory procedure.
(At a minimum, you should show all of your work and calculations for Mixture A at the bottom of this page or on
a separate page, and hand this work in with your Prelab.)
Experiment 9 13
TF: __________________ Name: __________________________
Experiment 9 14
TF: __________________ Name: __________________________
Postlab
This Postlab is due at 9:30 am on Tuesday May 19th.
In this lab you studied the kinetics of the following chemical reaction, the iodination of cyclohexanone:
I3 + cyclohexanone ! 2-iodocyclohexanone + H+ + 2 I
1. Write the rate law for this reaction that you determined from your experimental data in the lab.
(This should be copied from your answer to problem 12 on page 12 of the Lab Report.)
Rate Law =
2. A proposed mechanism for the iodination of cyclohexanone is included on the next page. Some of the reactants,
intermediates, and products have been labeled with letters (A, B, C, D, E) so that you dont have to write out Lewis
structures for all the species. Derive the rate law expected for this mechanism in the following circumstances:
a) Step 1 is the slowest step, and the remaining steps are fast.
Rate =
b) Step 2 is the slowest step, Step 1 is in rapid equilibrium, and the remaining steps are fast.
Rate =
c) Step 3 is the slowest step, Steps 1 and 2 are in rapid equilibrium, and Step 4 is fast.
Rate =
3. You have now evaluated this proposed mechanism by determining the rate law using several different
possibilities for the rate-determining step. Are any of these predicted rate laws consistent with your
experimentally-determined rate law for this reaction? If so, which step in this proposed mechanism is the rate-
determining step?
Experiment 9 15
Proposed Mechanism for Iodination of Cyclohexanone
O OH +
H H H H
C C
H C C H k1 H C C H
A + H+ B Step 1
k-1
H C C H H C C H
C C
H H H H
H H H H
+
OH OH
H H H
C C H
H C C H k2 H C C
B C + H+ Step 2
H C C H k-2 H C C H
C C
H H H H
H H H H
OH OH +
H H I
C H C
H C C H C C H
k3 Step 3
C + I3 - D + 2I-
H C C H H C C H
C C
H H H H
H H H H
OH + O
H I H I
C C
H C C H k4 H C C H
+ H+ Step 4
D k-4
E
H C C H H C C H
C C
H H H H
H H H H
Overall Reaction: A + I3 E + H+ + 2I
Experiment 9 16