PHYS 1 46

PHYS 1 Bromination of Acetone

1 week
PHYS 1

BACKGROUND READING

In this experiment, you will determine the rate law for the bromination of acetone in an acidic medium.
Determining the rate law is an important step in elucidating the mechanism of a reaction. This experiment
demonstrates that the rate law does not necessarily bear any simple relationship to the stoichiometric
equation for the reaction. You will learn how the rate law is determined from the kinetics data and what
implication it has for the reaction mechanism.

The stoichiometric equation for the bromination of acetone is shown below (Eq. 1).

The reaction rate is known to increase with the concentration of H+ in acidic medium or with OH- in basic
solution. Since the balanced equation for the reaction occurring in the acidic medium involves H+ as a
product; one would anticipate an increasing reaction rate in the course of experiments carried out in
unbuffered solutions.

The rate of halogenation of acetone is independent of halogen concentration except at very high acidities
(low pH) and low halogen concentrations. The rates of reaction with different halogens (Cl2, Br2 and I2) are
identical and the same as the rate of racemization of optically active ketones. These facts can be
reconciled with the following mechanism (Eqs. 2-4).
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The rate equation for the above mechanism can be solved for d[SBr]/dt or –d[Br2]/dt under steady-state
conditions and yields equation 5.

This equation takes on a simpler form if the enol (HS), which is formed after the first two steps, reacts
more rapidly with the halogen than with the hydrogen ion; k3[Br2] >> k-2[H3O+]. Under such a condition
the rate law takes the form

This is exactly what one observes experimentally by measuring the UV-Visible absorption of the solution,
provided that [Br2] > 10-4 M. We can see from the above simplified rate law that the overall reaction is
first-order in the acid and ketone but independent of bromine concentration, i.e., zero-order in bromine.
The observed second-order rate constant is the product of k-2 and the keto-enol equilibrium constant,
Kenol.

NOTE: the equilibrium constant Kenol can be expressed in terms of rate constants from reactions 1 and 2
(Eq. 7).
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EXPERIMENTAL PROCEDURE

Stock Solutions

• [CH3COCH3] = 3.0 M; bottle of pure acetone will be supplied. Calculate the amount of acetone needed
to prepare a 3.0 M acetone solution in 250 mL water. Use a 250 mL volumetric flask.

• [Br2] = (approximate) 0.01-0.02 M will be supplied, but you should determine the concentration of
bromine solution using absorbance of bromine at 400 nm.

ON-LINE LAB – You have been provided with an absorption scan in your Data File that can be used to
determine [Br2].

• [H3O+] = 1.0 M; supplied.

Operating Instructions for the Cary UV Spectrophotometer

1. First measurement (1): absorption spectrum of the diluted bromine stock solution in order to
determine the actual concentration of your bromine solution.
ON-LINE LAB: You will get an absorption spectrum of bromine and in the Excel file (tab 1) you can
determine what the absorbance is at 400 nm by looking up the y-value that corresponds to the x-value
of 400 nm.
2. Kinetics Measurements (12): You will use the Kinetics shortcut to obtain the data for the reaction
kinetics portion of the experiment. You will perform a measurement on the 12 different solutions.
ON-LINE LAB: You will get the data for the 12 kinetic runs in your Excel file (tab 2). To get the rate of
each of the kinetic runs, calculate the slope of each of the curves by performing a linear fit. A sample
printer output of the data is included in your Lab Book Notes document.

Figure 1: A Typical CARY-UV window.

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First measurement (1): Bromine Concentration Determination

To start the experiment, complete the following preparation steps:

1. On the main PC desktop open the Cary WinUV folder. Select the Scan shortcut;
2. Select the Setup button near the upper left corner of the application window;
3. Set the Start value to 650 nm and the Stop value to 360 nm (on-line lab 295 nm);
4. In the Options menu, activate the Individual data flag in the Display Options region;
5. Finish the Setup by selecting OK.
6. Dilute the supplied bromine stock solution by a factor of 10 (pipette 1 mL bromine solution into
a 10 mL volumetric flask and add water to the mark). Transfer an adequate amount of diluted
bromine solution into the 1 cm cuvette and place it into the cell compartment of the
spectrophotometer;
7. Place the cuvette in position 1 with the frosted side of the cuvette facing you;
8. Select the Start button in the top centre portion of the application window;
9. Select the current year’s folder on the desktop, enter a detailed filename and select Save; Save
the file also in Save Data as Spreadsheet Ascii(*.CSV) format appropriate for graphing data in your
lab report.
10. Enter a sample name and select OK;
11. When the run has ended, select Finish in the pop-up window for next Sample Name;
12. Move the mouse on to the UV spectrum at the 400 nm part of the curve;
13. Click on the right mouse button and choose Print XY point in the pop-up options;
14. Select Print in the lower left corner of the application window. Set printer HP LaserJet P1006,
select OK from the Print box in the printing menu. Calculate the concentration of diluted bromine
solution using 160 L mole-1 cm-1 at 400 nm as extinction coefficient. Report the concentration of
bromine stock solution to your demonstrator. Discard this diluted bromine solution and use only
the stock bromine solution in your kinetics runs. Keep the stock bromine solution stoppered at all
times;
15. Close the application by selecting File in the upper left corner and then Exit.
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Kinetics Measurements (12): Solution Preparation

To prepare the first solution for the kinetic study, follow the steps below:
1. Pipette 5 mL of stock solution of acetone into a 150 mL Erlenmeyer flask.
2. Add 10 mL of stock solution of H3O+ (NOT BROMINE, why?).
3. Add 25 mL of water from the burette.
4. To start the reaction, add 10 mL of the bromine stock solution.
5. Quickly transfer a portion of this reaction mixture into 1-cm sample cell. Do not forget to cover the cell
with a stopper.
6. Proceed with the kinetics measurement using the Cary UV-Vis as outlined in the section below.

For the next series of runs, vary the amount of stock solution of acetone (10 mL, 15 mL and 20 mL) keeping
the same volume of Br2 and H3O+ and always make up the total volume to 50 mL by adding water (water
should be added prior to addition of the Br2 solution). Thus, you should have four runs for different initial
concentrations of acetone while keeping the initial concentrations of Br2 and H3O+ the same. Follow the
same procedure for the other two variables, H3O+ and Br2 (e.g. runs 5-8, would have 5 mL, 10 mL, 15 mL
and 20 mL of H3O+ respectively). For your pre-lab make sure to fill in the table below.

Kinetics Measurements (12): UV-Vis Operation

To proceed with the kinetics study, follow the steps below:

1. Select the Kinetics shortcut;
2. Select the Setup button near the upper left corner of the application window;
3. Set the wavelength to 400 nm;
4. Set Stop (min.) to 2.00;
5. In the Reports Menu enter your names and any relevant comments;
6. In the Analyze Menu set Stop to 2 min. and order to Zero;
7. Select OK;
8. Select the Start button in the top centre portion of the application window;
9. Enter a detailed filename and find the current year’s folder on the desktop to Save your file.
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10. Prepare the reaction mixture (see EXAMPLE OF TYPICAL RUN). Upon adding bromine, quickly transfer
an adequate amount of the reaction mixture into a 1cm cuvette. Do not forget to cover the cuvette
with a Teflon stopper;
11. Place the cuvette in position 1 with the frosted side of the cuvette facing you;
12. Enter Sample 1 under Load Sample and select OK;
13. Select OK in the countdown pop-up window;
14. When the run has ended, select Clear Report and then Recalculate in the lower left corner of the
application window and select OK;
15. Select Print. (After you print the data for the first sample, you may see that it is only necessary to
print 1 page.);
16. Remove the current sample and rinse out the cuvette with distilled water;
17. Go to Step 8 and repeat the process.
18. You will need raw data files to prepare plots for your lab report. When all runs are complete, the
raw data can be exported to your flash drive. Go to File and select Save As. In the Files of type
dropdown menu, select Spreadsheet Ascii(*.CSV). Find your flash drive and click Save.

DATA ANALYSIS

To analyse the experimental data, follow the step

1. Graph the absorption of bromine and provide the calculation for the concentration of the bromine
stock solution. ON-LINE LAB: The data for the bromine absorption is given in the Excel file (tab 1).
2. ON-LINE LAB: Use the raw data of the kinetic runs to extract the corresponding initial rates by finding
the slope through linear fits.
3. Table of initial concentrations of all reactants with corresponding initial rates (AU/sec and M/s);
4. Plot log (initial rate) versus log (initial concentration) and establish the order of reaction with respect
to acetone, acid and bromine and show the slopes. Use linear regression. Do your observations agree
with the proposed mechanism?
5. NOTE: On your graphs, do not forget to include error bars. Be careful how you calculate the error in
the log(concentration) and log(initial rate) terms. Consult the lecture ppt for more details.
6. Use either acetone or acid variation runs and plot initial rate against initial concentration. Obtain the
slope of this line and the statistics of the fit from LINEST. What does this slope represent? Can you
identify this slope with the various rate constants of the elementary steps proposed in the
mechanism?
7. From the enolization constant Kenol = 2.5 × 10-6 (Bell & Yates 1962), the rate constant obtained from
the experiment, and k3 = 3.7 × 106 L mol-1 sec-1, calculate and tabulate the rates of reaction using the
general rate law and compare them with the rates obtained experimentally. Always give proper
units. NOTE: You are required to calculate errors. The experimental errors are provided by the
instrument (ON-LINE LAB: provided in the table in the lab book document), but you are still required
to give the error for the theoretical rate).
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LAB REPORT

ABSTRACT
Aim to present final and key results of your study (technique used, rate law determined). Use concise
language and ensure to communicate if your findings are consistent or inconsistent with the expected
outcome.

INTRODUCTION
An introduction that adequately sets the stage for the specific context and relevance of the experimental
aim. State the purpose of the experiment and provide enough background information to describe why
this study is important in the context of known literature.

• Present the theoretical background and the derivation of the steady state approximation for this
reaction
• Explanation how the differential method will be used to determine the reaction orders
• Elaborate briefly on relevant experimental methods, such as UV-Vis absorption and Beer’s Law as
they will be applied in the extraction of information

EXPERIMENTAL
Briefly describe the experimental procedure. Consult the lab manual and the details from the lab book
document (ON-LINE LAB) for relevant specifics. Note any observations and the apparatus used for any
measurements.

ON-LINE LAB In the lab book document, you have a list of all the materials that you would have been
provided with in the lab. Pay attention to the glassware that is available and rationalize how you would
make solutions.

RESULTS AND DISCUSSION

For results follow the details in the data analysis section and the instructions given in tutorial.
The discussion section should contain statements referring to the order of the reaction and comparison
of the experimental and theoretical rates. Expand your results with a discussion that puts your results in
perspective. Do you expect that halogenation with chlorine or iodine would show similar kinetics as the
bromination that you have studied? Provide a theoretical reasoning to this question and support your
conclusion with a literature comparison.
Please read what you wrote and see if it makes sense. Often students write statements reflecting what is
stated in the lab manual rather than the trends derived from their experimental results. Your mark will
depend on the CORRECT interpretation of your results and not on what you are supposed to get.
CONCLUSION
Brief. Comment on method and what was extracted, put results in perspective.
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REFERENCES
Minimum of 5 good references (not counting the lab manual) as in-text citations. While you can use all
the references provided in the lab manual, only 2 will count towards your minimum of 5. Make sure to
follow Chemical Reviews style guidelines.

*NOTE: If this is your first physical chemistry lab, then you have to write it in Journal Article Format – see eClass for details

Abstract Introduction Experimental Results & Discussion Conclusion References Writing Style
5% 15% 5% 55% 10% 5% 5%

PRELAB QUESTIONS
1. [1] The UV spectrophotometer gives a linear response between 0.0022 – 3.3 AU. What does it mean
if your reading is outside this range?
2. [3] Propose a mechanism for a base catalysed bromination of acetone and derive the general rate
equation (#5) for both base and acid catalysed systems.
3. [1] Under what condition is the reaction zero-order in bromine and what is the rate-determining step?
4. [1] Explain under what condition will the rate of the reaction depend on the concentration of bromine?
Is it still zero order with respect to [Br2]? Explain.
5. [1] Prepare a table listing the quantities of all solutions required for each run.
6. [1] Show Beer’s law and define each term.
7. [1] Why is bromine the last solution to be added prior to acquiring the UV data?
8. [1] What are the potential health effects as listed by the Material Safety Data Sheets for bromine? Be
sure to address the following categories: inhalation, ingestion, skin contact and eye contact.

REFERENCES
GENERAL KINETICS

1. Engel, T.; Reid, P. Thermodynamics, Statistical Thermodynamics, and Kinetics, 4th ed.; Pearson
Education Inc., New York, 2019, pp. 493-520.

GENERAL - CATALYZED HALOGENATION OF ACETONE

2. Archer, G.; Bell, R. P. J. Chem. Soc. 1959, 3228-3230.

3. Bell, R. P.; Yates, K. J. Chem. Soc. 1962, 1927-1933.
4. Bell, R. P.; Davis, G. G. J. Chem. Soc. 1964, 902-904.
5. Bell, R. P.; Smith, P. W. J. Chem. Soc. 1966, 241-243.
6. Tapuhi, E.; Jencks, W. P. J. Am. Chem. Soc. 1982, 104, 5765.
7. Birk, J. P.; Walters, D. L. J. Chem. Ed. 1992, 69, 585-587.