Chemical Kinetics: The Iodine Clock

Based on an experiment by Jim Klent of Ohlone College

Please consult Oxtoby, Gillis and Campion, Principles of Modern Chemistry (8th Edition) Ch. 18
Chemical Kinetics before performing this experiment.
During this experiment you will use the method of initial rates to determine the rate law, including
the value of the rate constant and orders of reaction with respect to each reactant, for the “iodine
clock” reaction at room temperature.

Introduction
Kinetics
The study of kinetics is central to all of chemistry. While thermodynamics predict the most
energetically favorable state for a system, kinetics tells us how fast the system will reach that state.
It also allows us to envision how the reaction proceeds mechanistically. Indeed, in many cases it
is the kinetics, not the relative thermodynamics, that determine the efficiency of a chemical
process.

Rates
The rate of a reaction is defined as the change in the concentration of a species in the reaction per
unit time. In other words, the rate of a reaction is an expression of how quickly the products are
produced and how quickly the reactants are consumed. We can determine the rate of a reaction by
𝑑[𝑃]
measuring the increase in the concentration of a product ( ) or decrease in concentration of a
𝑑𝑡
𝑑[𝑅]
reactant ( ) as a function of time. For the generic reaction,
𝑑𝑡

2𝐴 + 𝐵 → 𝐶

there are two moles of substance A reacting with one mole of substance B each time one mole of
substance C is formed. Thus, the rate, R, for this reaction may be expressed by any of the following:

1 𝑑[𝐴] 𝑑[𝐵] 𝑑[𝐶]

𝑅=− =− =+
2 𝑑𝑡 𝑑𝑡 𝑑𝑡
where we divide by the stoichiometric coefficient since the overall rate of reaction must be the
same regardless of which species we examine. Another way to think of this is that substance A is
consumed twice as fast as substance B, and twice as fast as substance C is produced. Substance B
is consumed at the same rate substance C is produced. For most chemical reactions, changing the
concentrations of the reactants will change the rate of the reaction, though the specific effect
depends on the details of the reaction mechanism, which is the series of specific chemical
interactions that occur as the reaction proceeds.

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Rate Laws

A rate law or rate equation relates the concentration of chemical species involved in a reaction to
the rate of the reaction. As more reactant molecules (or ions, or atoms) are packed into a fixed
volume (i.e., the concentration increases) they will encounter each other more frequently,
presenting more opportunities to react. At first, you might predict that the rate of a reaction is
proportional to the concentrations of each of the species involved; this is not always the case. In
many reactions, a rate-limiting step in the reaction mechanism (e.g., enzyme kinetics or catalysis)
determines the overall rate and the addition of more reactants has little to no effect. In other cases,
changing concentration of any one reactant can have a significant effect on the overall reaction
rate.

In general, we can write the overall rate equation as a product of the concentrations of the various
species involved, each raised to some power:

𝑅 = 𝑘[𝐴]𝑥 [𝐵]𝑦 (1)

where 𝑘 is the rate constant, which mostly depends on temperature. Here, x and y represent the
order of the reaction with respect to reactants A and B. It should be noted that x and y (except in
the case of elementary reactions) are not necessarily proportional to the stoichiometric ratios of A
and B. The overall order of a reaction is the sum of the orders of the individual reactants (e.g., x
+ y in equation 1 above).

In this experiment, you will study the net ionic reaction:

6 𝐼 − (𝑎𝑞) + 𝐵𝑟𝑂3− (𝑎𝑞) + 6 𝐻 + (𝑎𝑞) → 3 𝐼2 (𝑎𝑞) + 𝐵𝑟 − (𝑎𝑞) + 3 𝐻2 𝑂 (𝑙) (2)

For this reaction, the generic rate law can be expressed as:

𝑅𝑎𝑡𝑒 = 𝑘[𝐼 − ]𝑥 [𝐵𝑟𝑂3− ]𝑦 [𝐻 + ] 𝑧 (3)

To determine the orders (x, y, and z), we will use the method of initial rates, where the rate is
measured for a short time immediately after a reaction is started using known concentrations of
reactants. The reaction rate is then measured a second time, this time changing the concentration
of one species (e.g., I–,) by a known factor while holding the others constant. In the example below
we will double the concentration of I–. From the change in the measured overall rate, the order
with respect to that individual reactant can be calculated by dividing the two rate expressions:

𝑅𝑎𝑡𝑒1 𝑘[𝐼 − ]𝑥 [𝐵𝑟𝑂3− ]𝑦 [𝐻 + ]𝑧

= (4)
𝑅𝑎𝑡𝑒2 𝑘(2[𝐼 − ])𝑥 [𝐵𝑟𝑂3− ]𝑦 [𝐻 + ]𝑧

Since we only doubled the concentration of I− between experiments (everything else was held
constant) and rate is inversely proportional to time (rate ∝ time-1), we can simplify this
expression to obtain:

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 𝑅𝑎𝑡𝑒1 [𝐼 − ]𝑥 1 𝑥 𝑡𝑖𝑚𝑒2
= (2[𝐼−])𝑥 = ( ) = (5)
𝑅𝑎𝑡𝑒2 2 𝑡𝑖𝑚𝑒1

We can now solve for 𝑥 in terms of the overall reaction times.

To time the reaction, we will make use of the facts that iodine (I2) reacts with starch to form a blue
complex and iodine will also react (at a faster rate) with thiosulfate ions (S2O32-) to form iodide
(I-), which does not react with starch.

𝐼2 (𝑎𝑞) + 𝑠𝑡𝑎𝑟𝑐ℎ → 𝑏𝑙𝑢𝑒 𝑐𝑜𝑚𝑝𝑙𝑒𝑥 (fast) (6)

𝐼2 (𝑎𝑞) + 2 𝑆2 𝑂32− (𝑎𝑞) → 2 𝐼 − (𝑎𝑞) + 𝑆4 𝑂62− (𝑎𝑞) (very fast) (7)

Thus, when thiosulfate ions are present in solution, the second reaction will dominate, and the
solution will remain colorless. Once the thiosulfate ions are all consumed, the solution will
immediately become blue. The time it takes to consume the thiosulfate ions depends on the rate at
which the overall reaction produces I2. Thus, we have a “clock” to measure the rate of reaction.

Note: The time elapsed before the appearance of the blue color is inversely proportional to the
overall rate of reaction and does not reflect the time it takes for six individual molecules of
thiosulfate ions to react.

The rate constant, k, and thus an actual reaction rate, can be calculated if the quantity of thiosulfate
and the reactant orders x, y, and z are known. In this experiment, we will start with a precisely
known concentration of thiosulfate (1.00 × 10–4 M) and stop the “clock” when [S2O32-] becomes
zero, as indicated by the appearance of the blue color. By adding a known amount of thiosulfate
ion to our reaction mixtures we can conclude how much I2 was produced prior to the appearance
of the color change and calculate a value for the rate that resulted from our initial concentrations.

Thus, the rate of reaction can be expressed as:

1 ∆[𝑆2 𝑂32− ]
𝑅𝑎𝑡𝑒 = − ( ) ( ) = 𝑘[𝐼 − ]𝑥 [𝐵𝑟𝑂3− ]𝑦 [𝐻 + ]𝑧 (8)
6 ∆𝑡

where we divide the thiosulfate concentration by six because there are three iodine molecules
produced each time the reaction is run, and two thiosulfates are required to react with every iodine
molecule formed.

Since we will conduct several trials to find the reaction orders, we can use each of these trials to
obtain an average value for the rate constant, k.

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 References

[1] D. W. Oxtoby, H. P. Gillis and L. J. Butler, "Ch. 18 Chemical Kinetics," in Principles of

Modern Chemistry, 8th ed., Boston, Massachusetts: Cengage Learning, 2016, pp. 754-806.

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 Prelab Questions
1. The following initial rate data were obtained for the reaction:

2 𝑁𝑂 (𝑔) + 𝐵𝑟2 (𝑔) → 2 𝑁𝑂𝐵𝑟 (𝑔)

Trial [𝑁𝑂] (𝑀) [𝐵𝑟2 ] (𝑀) 𝑅𝑎𝑡𝑒 (𝑀 ∙ 𝑚𝑖𝑛−1 )

1 1.0 1.0 1.30 × 10−3

2 2.0 1.0 5.20 × 10−3

3 1.0 2.0 2.60 × 10−3

Determine the reaction rate law and the rate constant (with units) using the method of initial
rates described in the Introduction. Show ALL work.

Note: For these data, actual rates, not reaction times, are measured.

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 Materials and Methods
Work in groups of 2.

Purpose
You will use the method of initial rates to determine the rate law, including orders for all the
reactants and the value of the rate constant, for the “clock” reaction between iodide and bromate
in acid:
6 𝐼 − (𝑎𝑞) + 𝐵𝑟𝑂3− (𝑎𝑞) + 6 𝐻 + (𝑎𝑞) → 3 𝐼2 (𝑎𝑞) + 𝐵𝑟 − (𝑎𝑞) + 3 𝐻2 𝑂 (𝑙)
Materials
Equipment

volumetric pipet, 5 mL a small beaker (50 – 100 mL)

volumetric pipet, 10 mL a stopwatch
several Erlenmeyer flasks, (100 – 250 mL) a thermometer

Chemicals

Potassium iodide, 10 mM KI CAS 7681-11-0 150 mL

This solution is considered nonhazardous. However, all lab
Hazards/Safety chemicals should be handled with care to avoid unpredictable
reactions among chemicals.

Sodium thiosulfate, 1 mM Na2S2O3 CAS 7772-98-7 120 mL

This solution is considered nonhazardous. However, all lab
Hazards/Safety chemicals should be handled with care to avoid unpredictable
reactions among chemicals.

Potassium bromate, 40 mM KBrO3 CAS 7758-01-2 150 mL

Danger! Solutions of potassium bromate may cause skin and serious eye
damage, corrosion or irritation. This solution is also acutely toxic
and harmful if swallowed. Handle with extreme care and take
only what you need.

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 Hydrochloric acid, 0.1 M HCl CAS 7647-01-0 150 mL
Danger! Hydrochloric acid solutions can cause severe skin burns and eye
damage. Do not breathe mist, vapors or spray. May cause
respiratory irritation. This solution is also acutely toxic and
harmful if swallowed. Handle with extreme care and take only
what you need.

Starch indicator, 1% w/v

Soluble Starch (1%) (C6H10O5)n CAS 9005-84-9
Salicylic Acid (0.1%) C7H6O3 CAS 69-72-7 5 mL
Warning!
May cause eye, skin, gastrointestinal and respiratory tract
irritation.

Procedure
You will perform three replicate measurements on each of the four different reaction mixtures
listed in Table 1 below. Each mixture contains the reactants at varied, but controlled
concentrations. For each reaction mixture you will first prepare two solutions, A and B. Solution
A will contain potassium iodide, sodium thiosulfate and water. Solution B will contain potassium
bromate, hydrochloric acid, and starch indicator. Pay careful attention because solutions A and B
are different for each reaction mixture.

You will initiate the clock reaction by mixing solutions A and B carefully and quickly while
starting a stopwatch. When the resulting mixture turns dark (due to formation of the iodine-starch
complex) you will stop the stopwatch and record the elapsed time.
Table 1. Reaction mixtures for kinetic trials

Solution A Solution B
Reaction 0.010 M H2O 0.001 M 0.040 M 0.100 M 1% starch
Mixture KI (mL) (mL) Na2S2O3 (mL) KBrO3 (mL) HCl (mL) indicator
1 10.00 10.00 10.00 10.00 10.00 10 drops
2 20.00 0.00 10.00 10.00 10.00 10 drops
3 10.00 0.00 10.00 20.00 10.00 10 drops
4 10.00 0.00 10.00 10.00 20.00 10 drops

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1. Fill a small beaker (50 to 100 mL) with distilled water. Allow this water to equilibrate to room
temperature for 30 minutes as you make other preparations. This water will be added to
solution 1-A and must be at the same temperature as the rest of the solutions. You can begin
your measurements on reaction mixtures 2, 3, and 4 while you wait for the water for mixture
1 to equilibrate to room temperature.

2. Retrieve your reagents (the amount you will need of each is listed in the chemicals section
above) in sufficiently sized vessels (beakers or flasks are OK). Make sure your vessels are
clean, dry, and labeled before filling.

• Record the exact concentrations of the stock solutions as reported by the stockroom.

• Record the temperature of the solutions you obtained to the nearest 0.1 ºC and confirm
they are the same. Clean and dry the thermometer between solutions to prevent cross
contamination.

• Do not do any measurements on mixture 1 until your distilled water sample is the same
temperature as your other solutions.

3. Prepare solutions A and B as noted in Table 1 for the reaction mixture you are analyzing.

• Each mixture should be carefully prepared in a clean and dry 100 to 250 mL
Erlenmeyer flask.

• Measure out and dispense the component solutions using 5 or 10 mL volumetric pipets.
Practice good quantitative pipetting technique by making sure the pipet has been rinsed
with the solution you are measuring before dispensing. Ideally you can dedicate a single
pipet to each solution to avoid cross contamination and to minimize the number of pipet
rinses.

• Don’t forget to add the starch to solution B or you will not see when the reaction has
reached completion. Note: Starch can settle out of solution—give the starch dropper
bottle a good shake before dispensing.

4. Pour solution B into the flask with solution A carefully and quickly while starting a stopwatch.
After emptying the flask containing solution B swirl the mixture for about 10 seconds and
then set the reaction flask (that originally contained only solution A) down on a piece of white
paper to aid in visualization of the iodine-starch complex.

5. Using the stopwatch, measure the reaction time to the nearest second. Start timing at the
moment of transfer (step 4, above) and stop timing when the dark colored iodine-starch
complex first appears. Record the time it took for the iodine-starch complex to appear for
each trial.

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6. Repeat the above procedure, recording your data as you go, until you have performed three
trials of each reaction mixture (1 through 4). It is recommended that you get data for each
reaction mixture before repeating measurements in case you run out of time.

7. Calculate the reactant concentrations in each final solution (solution A + solution B) for each
reaction mixture (1 through 4). Report your values in units of molarity.

8. Calculate the reaction rate for each trial. Use the data to calculate the average rate (with proper
units) of each reaction mixture (1 through 4) including 95% confidence intervals.

9. Use your data to determine the rate law for the reaction using the method of initial rates
described in the Introduction. Round reaction orders to the nearest rational number (e.g.,
½, 1, 2, etc.). Show your calculations in your lab notebook.

10. Determine the rate constant, 𝑘 (with units), for each reaction mixture and the average rate
constant for the reaction. Show your calculations in your lab notebook.

Cleanup and Waste Disposal

1. Dispose of all reaction mixtures and excess reagent solutions in the “All Solutions” waste
bottle in the fume hood. Remember to log your waste – you should know the volume of each
reagent solution used from the procedure and your lab notebook.

2. Dispose of any chemically contaminated solid waste (e.g., Kim-wipes, paper towels, plastic
weighing boats, disposable pipets, gloves) in the large round blue drum designated for
contaminated solid waste.

3. Rinse all glassware used thoroughly. Collect the first rinse in a waste beaker for disposal in
the “All Solutions” waste bottle – log this waste as water. Dry the glassware before putting it
away.

4. Return any borrowed equipment (5.00 mL and 10.00 mL volumetric pipets, stopwatches and
any other checked-out equipment) to the location you borrowed it from – either to the ISF
stockroom window (221 Latimer) OR to the side bench or fume hood in your lab room. Do
NOT lock borrowed equipment in your lockers.

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 Report Sheet
Name_______________________________ Partner(s)_____________________________

Answer questions in TWO sentences or less.

1. Complete the following table with your raw data and calculate average reaction times for each
reaction mixture.

Reaction Reaction Times (s)

Average
Mixture Time (s)
Trial 1 Trial 2 Trial 3

2. Complete the following table of reactant concentrations in the final mixture and calculate
reaction rates for each reaction mixture using the equations given in the lab manual.

Reaction
[𝐼 − ] (M) [𝐵𝑟𝑂3− ] (M) [𝐻 + ] (M) Rate (M/s)
Mixture

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3. Determine reaction orders for the rate law expression using the method of initial rates. Round
reaction orders to the nearest whole number. Show all calculations (attach additional pages if
necessary).

Rate = 𝑘[𝐼− ]𝑥 [𝐵𝑟𝑂3− ]𝑦 [𝐻+ ]𝑧 𝑥 =______

𝑦 =______

𝑧 =______

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4. Determine the rate constant (𝑘) at room temperature for each reaction mixture and calculate
the average with correct units. Show calculations for Reaction Mixture 1 in the space provided
below.

Reaction
Rate constant, 𝑘
Mixture

Average

5. Perform a Grubbs Test for an outlier to check for possible rejection of outlier data. (Harris,
9th Ed., pp. 80-81)

6. Compute a 95% confidence interval for the rate constant, 𝑘, at room temperature. Show all
work. (Harris, 9th Ed., pp. 71-74)

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7. Does your rate law have the same orders as the stoichiometric coefficients in the overall
reaction? What does this tell you about the reaction mechanism?

8. Is it possible to write the reaction mechanism from the data obtained in this lab?

If so, write the mechanism, and use your data to support it.

If not, explain what additional information is required to determine the mechanism.

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