Experiment

18
Kinetics of a Reaction
Introduction:
The speed of a chemical process can determine the usefulness of a process. A very slow
reaction speed may not be practical, a very quick reaction speed may be dangerous.
Measuring and controlling reaction rates makes it possible for chemists and engineers to
make a variety of products, from antibiotics to fertilizers, in a safe and efficient manner.
We will investigate how the rate of a reaction can be measured and how reaction
conditions affect reaction rates.

Background:
This experiment is designed to study the kinetics of a chemical reaction. The reaction
involves the oxidation of iodide ions by bromate ions in the presence of acid:

6I-(aq) + BrO3-(aq) + 6H+(aq)  3I2(aq) + Br-(aq) + 3H2O(l) (reaction 1)

The reaction is somewhat slow at room temperature. As we have studied, reaction rate
depends on the concentration of the reactants and the temperature of the system. The rate
law for this reaction is a mathematical expression that relates the reaction rate to the
concentration of the reactants. If the reaction rate is expressed as the rate of decrease in
concentration of bromate ion, the rate law has the form:

 [BrO3 - ]
Rate   k[ I - ] x [ BrO3 - ] y [ H  ] z (equation 1)
t

The rate is equal to the change in concentration of the bromate ion divided by the change
in time for the reaction to occur. The rate constant will change depending upon the
temperature of the system. The concentration of each substance will be shown to affect
the reaction rate as a function of its reaction order, represented by the exponents x, y, and
z. The total rate law for the process is determined by measuring the rate, evaluating the
rate constant, and determining the reaction order for each reactant in the process.

To find the rate of reaction a method is needed to measure the rate at which one of the
reactants is consumed, or the rate at which one of the products is formed. In this
experiment, the rate of reaction will be measured based on the rate of iodine formation.
The reaction will be carried out in the presence of thiosulfate ions, which react with
iodine as follows:

I2(aq) + 2S2O32-(aq)  2I-(aq) + S4O62-(aq) (reaction 2)

Reaction 1 is somewhat slow. Reaction 2 is extremely fast, meaning that as soon as the
iodine is formed in reaction 1, it is consumed by reaction 2. Reaction 2 will proceed until
all the thiosulfate is consumed, after which an increases in iodine concentration may be
observed in the solution. The addition of a starch indicator can reveal the presence of

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 Experiment 18

iodine by the observation of a deep blue-black color that is formed as a result of the
iodine-starch complex.

Carrying out reaction 1 in the presence of thiosulfate ion creates a chemical clock – when
thiosulfate is consumed, the reaction turns blue almost instantly.

In this laboratory procedure, all the reactions use the same quantity of thiosulfate ion. The
blue color appears when all thiosulfate is consumed. An examination of the reactions 1
and 2 shows that six moles of thiosulfate are needed to react with the three moles of
iodine that are formed from one mole of bromate in reaction 1. Knowing the amount of
thiosulfate used, it is possible to calculate both the amount of iodine that is formed and
the amount of bromate that has reacted at the time of the color change. The reaction rate
is expressed as the decrease in concentration of bromate ion divided by the time it takes
for the blue color to appear.

There is an energy barrier that all reactants must overcome for a reaction to take place.
This energy can range from very low (almost zero) to hundreds of kilojoules per mole.
This energy barrier is known as activation energy (Ea). Reactants need to possess this
amount of energy both to overcome the repulsive electron cloud forces between
approaching molecules and to break the existing bonds in the reacting molecules. In
general, as the activation energy increases, so does the rate of reaction. The Arrhenius
equation relates the rate constant to the activation energy:

k  Ae -Ea/RT

“A” represents the frequency constant, related to the frequency of collision of reacting
particles, “R” is the universal gas law constant, and “T” is the Kelvin temperature of the
reacting system.

Catalysts are substances that speed up a reaction, but are not consumed in the reaction.
Catalysts wok by lowering the overall activation energy of the reaction, thus increasing
the rate of reaction.

The experiment is designed so that the amounts of reactants that are consumed are small
in comparison with the total quantities present. This means that the concentration of the
reactants is almost unchanged during the reaction, and therefore the reaction rate is
almost a constant during this time.

The experiment utilizes a microscale procedure. Only twelve drops of reactants delivered
from capillary droppers are used for each measurement. A special microscale
“shakedown” technique is used to mix the reactants. The steps involved are as follows:
1. Measure the volume of a drop of solution: This must be done to determine the
number of moles of thiosulfate ion in one drop. This allows the moles of
bromate ion that react to be calculated.
2. Determine the reaction rate and calculate the rate law: This is done by
carrying out an experiment at specific concentrations of each of the reactants

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Kinetics of a Reaction

and measuring the reaction rate. The concentration of one reactant is then
changed and the reaction rate change is observed. This is repeated for each
reactant. This data allows the calculation of the order of each reactant. Once
the orders are known, the value of the rate constant can be determined.
3. Determine the activation energy: Reaction rate generally increase as the
temperature goes up. By measuring how the rate changes as the temperature is
varied, the activation energy for the reaction ca be calculated. The natural log
of the Arrhenius equation is:

- Ea
ln k   ln A
RT

where ln k is the natural log of the rate constant, E a is the activation energy, R
is the universal gas constant, and T is measured in the Kelvin scale. A is the
frequency factor. This equation shows a linear relationship. A plot of k versus
1/T will produce a straight line with the slope equal to –Ea/R. By determining
the slope of this curve, the activation energy can be calculated.
4. Observe the effect of a catalyst on the rate of reaction: The catalyst used in
this experiment is a solution of copper (II) nitrate.

Experiment Overview:
The purpose of this experiment is to utilize a microscale technique to determine the total
rate law for the oxidation of iodide ions by bromate ions in the presence of an acid. There
are several steps in this experiment. The reaction order for each of the reactants must be
determined by varying the concentration of each reactant individually. Once the reaction
orders are determined, the rate constant is calculated. The activation energy must be
calculated by repeating the experiment at several temperatures and analyzing the results
graphically. Finally, a catalyst is added to the system so a change in rate may be observed.

Pre-Lab Questions:
Another version of the iodine clock reaction involves the reaction of iodide ions with
persulfate ions:

2I-(aq) + S2O82-(aq)  I2(aq) + 2SO42-(aq) (reaction 3)

The following rate data was collected by measuring the time required for the appearance
of the blue color due to the iodine-starch complex.
Trial [I-] (M) [S2O82-] (M) Reaction Time (s)
1 0.040 0.040 270
2 0.080 0.040 138
3 0.040 0.080 142

1. In each trial, the blue color appeared after 0.0020 M iodine (I 2) had been
produced. Calculate the reaction rate for each trial by dividing the concentration
of iodine formed by the reaction time.

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 Experiment 18

2. Compare trials 1 and 2 to determine the order of reaction with respect to iodide
ions. How did the concentration of iodide ions change in these two trials, and how
did the rate change as a result? What is the reaction order for iodide?
3. Which two trials should be compared to determine the reaction order of persulfate
ion? What is the reaction order of persulfate?
4. Write the rate law for this version of the iodine clock reaction. Could the rate law
have been predicted using the coefficients in the balanced chemical equation?
Explain.

Materials: cupric nitrate solution (0.1 M) Analytical balance(0.001g precision)

Distilled water
Hydrochloric acid solution (0.10 M)
Potassium iodide solution (0.010 M)
Potassium bromate solution (0.040 M)
Starch solution (2%)
Sodium thiosulfate solution (0.0010 M)
Cassette tape case
Timer, seconds
Beaker (10 mL or 50 mL)
Beral-type pipet with microtip
Cotton swabs for cleaning well plate
Reaction strips, 12-well
Thermometer, 0oC-100oC
Toothpicks for stirring
Trough for hot and cold water baths
Label tape, for pipets

Safety:
Hydrochloric acid in dilute solutions is severely irritating to skin and eyes and is slightly
toxic by ingestion and inhalation. Dilute copper (II) nitrate solution is irritating to skin,
eyes, and mucous membranes and slightly toxic by ingestion. Dilute potassium bromate
solution is irritating to body tissue and slightly toxic by ingestion.

Procedure:
Part I:
1. Obtain a microtip beral pipet. Fill the pipet with 3 mL of distilled water.
2. Mass a small beaker using an analytical balance. Record the mass in your data
table.
3. Holding the pipet vertically, deliver five drops of water into the beaker.
Record the total mass.
4. Add an additional five drops of water to the beaker. Record the total mass.
5. Deliver five more drops and again record the mass.

Part II: It is necessary to use consistently good technique to obtain reproducible data.
Hold pipets vertically and be sure no air bubbles are introduced. Since such small
quantities of reagents are used, it is very easy to repeat measurements. Calculation of the
reaction orders of reactants are all based on the values obtained for the first experiment –
be sure you have reproducible data from the beginning of the experiment. All other
experiments should be carried out at least twice.

The table that follows shows the reagent quantities to be used in carrying out the
reactions needed. It is important to use care in measuring out the solutions. Since the total
solution volume is quite small, even one extra drop can cause a substantial change in
concentration.

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Kinetics of a Reaction

Experiment KI, Distilled HCl, Starch, Na2S2O3, KBrO3,

Number 0.010 M water 0.10 M 2% 0.0010 M 0.040 M
1 2 drops 4 drops 2 drops 1 drop 1 drop 2 drops
2 4 drops 2 drops 2 drops 1 drop 1 drop 2 drops
3 6 drops 0 drops 2 drops 1 drop 1 drop 2 drops
4 2 drops 2 drops 2 drops 1 drop 1 drop 4 drops
5 2 drops 0 drops 2 drops 1 drop 1 drop 6 drops
6 2 drops 2 drops 4 drops 1 drop 1 drop 2 drops
7 2 drops 0 drops 6 drops 1 drop 1 drop 2 drops

A study of this Table shows that all experiments contain the same total number of drops
of solution. Only one drop of sodium thiosulfate and one drop of starch solution are
added to each well. In experiments 1, 2, and 3, the concentration of potassium iodide is
gradually increased while all other solution volumes remain constant. Experiments 1, 4,
and 5 have an increasing concentration of potassium bromate. Experiments 1, 6, and 7
show and increase in concentration of hydrochloric acid.

Read the entire procedure before beginning the experiment:

1. Obtain six microtip pipets and fold a piece of tape around the stem of each pipet.
Label the pipets KI, H2O, HCl, Starch, Na2S2O3, and KBrO3.
2. Fill each pipet with about 2 mL of the appropriate reagent.
3. Place the pipets in an opened cassette case for storage.
4. Obtain two clean, 12 well reaction strips and arrange them so that the numbers
can be read from left to right.
5. The first determination will vary the concentration of only the KI. Using the
following table as a guide, fill each numbered well in the first reaction strip with
the appropriate number of drops of the reagent listed. Mix the solution in each
well with a new toothpick. Each experiment in Table 1 will be run in triplicate.
Experiment #1 Experiment #2 Experiment #3
Well 1 2 3 4 5 6 7 8 9
Drops 0.010 M KI 2 2 2 4 4 4 6 6 6
Drops distilled water 4 4 4 2 2 2 0 0 0
Drops 0.10 M HCl 2 2 2 2 2 2 2 2 2
Drops 2% Starch 1 1 1 1 1 1 1 1 1
Drops 0.0010 M Na2S2O3 1 1 1 1 1 1 1 1 1

6. To well 1-9 in the second strip add 2 drops of 0.040 M KBrO3.

Experiment #1 Experiment #2 Experiment #3
Well 1 2 3 4 5 6 7 8 9
Drops 0.040 M KBrO3 2 2 2 2 2 2 2 2 2
7. Turn the second reaction strip upside down and place it on top of the first strip so
that the numbered wells are line up on top of one another. Start timing as soon as
the strips are combined.
8. In the Part II Data Table, record the time when the solution in each well turns
blue.

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 Experiment 18

9. When all the wells have turned blue, take the temperature of one of the reaction
solutions. Record this temperature for all the reactions in the Part II Data Table.
10. Rinse the contents of the well strips with warm water. Use a cotton swab to dry
the inside of each well.
11. Repeat this entire process (steps 4-10) for the following combinations that cover
experiments 4 and 5 and experiments 6 and 7, respectively.
Reaction Strip #1 Experiment #4 Experiment #5
Well 1 2 3 4 5 6
Drops 0.010 M KI 2 2 2 2 2 2
Drops distilled water 2 2 2 0 0 0
Drops 0.10 M HCl 2 2 2 2 2 2
Drops 2% Starch 1 1 1 1 1 1
Drops 0.0010 M Na2S2O3 1 1 1 1 1 1

Reaction Strip #2 Experiment #4 Experiment #5

Well 1 2 3 4 5 6
Drops 0.040 M KBrO3 4 4 4 6 6 6

Reaction Strip #1 Experiment #6 Experiment #7

Well 1 2 3 4 5 6
Drops 0.010 M KI 2 2 2 2 2 2
Drops distilled water 2 2 2 0 0 0
Drops 0.10 M HCl 4 4 4 6 6 6
Drops 2% starch 1 1 1 1 1 1
Drops 0.0010 M Na2S2O3 1 1 1 1 1 1

Reaction Strip #2 Experiment #6 Experiment #7

Well 1 2 3 4 5 6
Drops 0.040 M KBrO3 2 2 2 2 2 2

Part III: Determine the Activation Energy

In this part of the experiment, the reaction will be carried out at several different
temperatures using the concentrations given in Part II for Experiment #1. The
temperatures will be about 40, 20, and zero degrees Celsius, respectively. Use data from
Experiment #1 at room temperature for the second experiment.

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Kinetics of a Reaction

1. Prepare a shallow warm water bath of about 40 degrees Celsius.

2. Using the following table as a guide, fill each of the first six wells in the
reaction strip with the appropriate number of drops of the reagent listed. Mix
the solutions well with a new toothpick.
Well 1 2 3 4 5 6
Drops 0.010 M KI 2 2 2 2 2 2
Drops distilled water 4 4 4 4 4 4
Drops 0.10 M HCl 2 2 2 2 2 2
Drops 2% starch 1 1 1 1 1 1
Drops 0.0010 M Na2S2O3 1 1 1 1 1 1
3. Place the reaction strip in the warm water bath.
4. Fill the beral pipet labeled KBrO3 half-full with 0.040 M KBrO3 solution.
5. Place this pipet in the warm water bath for at least five minutes.
6. Measure the temperature of the water bath with a thermometer and record the
value in the Part III data table.
7. Take the pipet out of the water bath and dry the outside of the pipet.
8. With the reaction strip still in the warm water bath, add two drops of
potassium bromate solution to the first well, stir, and immediately start the
timer. Place the pipet back in the warm water bath.
9. Record the time, in seconds, when the blue color first appears.
10. Repeat steps 7-9 for the reaction in wells #2 and #3.
11. Remove the reaction strip and the pipet from the warm water bath.
12. Add ice cubes and water in a shallow pan to create a cold water bath.
13. Place both the reaction strip and beral pipet containing potassium bromate
solution into the cold water bath for at least five minutes. Measure the
temperature of the cold water bath and record this value in the Part III data
table.
14. Repeat steps 7-9 for wells #4, #5, and #6. Record the time, in seconds, for
each reaction in the Part III data table.

Part IV: Observe the Effect of a Catalyst on Reaction Rate

Repeat the procedure given in Part II for Experiment 1 only, but this time add 1 drop of
0.1 M copper (II) nitrate solution and only 3 drops of distilled water to the mixture. Fill
only the first reaction wells. The total volume will still be 12 drops. Record the reaction
times in the Part IV data table.

Data Tables:
Part I Data: Find the volume of one drop of solution
Mass of empty beaker (a) g
Trial 1 Mass of beaker plus 5 drops of water (b) g
Mass of first five drops of water (b) – (a) g

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 Experiment 18

Average mass of 1 drop of water g

Trial 2 Mass of beaker plus 10 drops of water (c) g
Mass of second 5 drops of water (c) – (b) g
Average mass of 1 drop of water g
Mass of beaker plus 15 drops of water (d) g
Trial 3
Mass of third 5 drops of water (d) –(c) g
Average mass of 1 drop of water g
Average mass of 1 drop of water (trials 1-3) g

Part II Data Table: Determine the Reaction Rate and Calculate the Rate Law
 Time, seconds 
Experiment # Trial 1 Trial 2 Trial 3 Average Temp, oC

Part III Data Table: Determine the Activation Energy

 Time of Reaction 

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Kinetics of a Reaction

Approx Measured Measured Measured Avg

Trial 1, Trial 2, Trial 3,
Temp, Temp, Temp, Temp-1, Time,
(s) (s) (s)
(oC) (oC) (K) (K-1) (s)

20
(May be taken
from Part II Exp
#1)

40

Part IV Data Table: Observe the Effect of a Catalyst on Reaction Rate

Average
Trial 1, s Trial 2, s Trial 3, s
Time, s

Uncatalyzed Reaction

Catalyzed Reaction

Calculations:

Part 1: Calculate the volume of one drop of solution. Assume the density of water to be
1.00 g/mL. Your final answer should be in liters.

Part IIa: Calculate the Rate

1. The rate will be expressed as –[BrO3-]/t. In each reaction there is one drop of
0.0010 M Na2S2O3 solution. Calculate the number of moles of thiosulfate present
in one drop.

1 drop = _______________ moles S2O32-

2. The blue color begins to appear when all of the thiosulfate ion is consumed.
Examination of reactions 1 and 2 (Background) allows us to calculate the moles
of bromate ion that react as all the thiosulfate ion is used up. Calculate the moles
of bromate ion consumed in this reaction.

Moles of BrO3- consumed = ________________ mol

3. Determine the value of -[BrO3-]. Each reaction has a total volume of 12 drops, so
this value may be calculated by determining the moles of bromate ion that reacted
and dividing by the volume of 12 drops of solution.

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 Experiment 18

Change in bromated ion concentration = ______________M

4. The reaction rate can be found by dividing the change in bromate ion
concentration by the change in time (measured in seconds during the experiment).
Enter the results of the rates of reaction for Experiments 1-7 in the table below:

Reaction Rate, M/s

Experiment #1

Experiment #2

Experiment #3

Experiment #4

Experiment #5

Experiment #6

Experiment #7

Part IIb: Calculate the Initial Concentrations

Calculate the initial concentration of each reactant for each experiment. These are the
concentrations of each reactant after all the reactants have been mixed, but before any

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Kinetics of a Reaction

reaction has taken place. This will not be the same as the concentration of the starting
solution because combining the reactants dilutes all of the solutes (you have increased the
total volume. On dilution, the number of moles of reactant stays the same, but the total
volume of the solution will increase. Because the volumes of the solutions are
proportional to the number of drops used, the number of drops may substitute for the
volumes of the solutions in the dilution formula: (#drops 1)(M1) = (#drops2)(M2). Find the
initial concentration of each reactant and record in the data table below:

[I-] (M) [BrO3-] (M) [H+] (M)

Exp #1

Exp #2

Exp #3

Exp #4

Exp #5

Exp #6

Exp #7

Part IIc: Calculate the Order of Each Reactant

The values for the reaction order of each reactant may be determined by analyzing our
reaction rate data. The experiment was designed so that the concentration of only one

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 Experiment 18

ions changes while the other concentrations remain constant. Comparing values in
experiments #1, #2, and #3, it is observed that Experiment #2 has double the iodide ion
concentration of Experiment #1, and Experiment #3 has triple the iodide ion
concentration as experiment #1. Substitute the concentration values for experiments #1
and #2 into the equation: Rate = k[I-]x[BrO3-]y[H+]z

Exp #1: Rate1 _______ = k[_____]x[_____]y[_____]z

Exp #2: Rate2 _______ = k[_____]x[_____]y[_____]z

Divide the first equation by the second. Notice that most of the terms will cancel
Rate1 [ ]x
algebraically, reducing the ratio to: 
Rate2 [ ]x
Divide and solve for x. Report the value to the nearest integer. Repeat the calculations
using experiments #1 and #3 to confirm the value for x. (Math Review: To solve for an
exponential value, take the logarithm of both sides of the equation.)

After confirming the value of x, repeat the same procedure using Experiments #1, #4, and
#5 to determine the value of y. Finally, using Experiments #1, #6, and #7, one may
calculate the value of z.

Part IId: Find the Rate Constant

Substitute data from each experiment into the rate law equation to find the value of k.
Report the average value of k (including proper units).

Experiment 1 2 3 4 5 6 7

Value of k

Average value of k = _______________

Part III: Calculate the Activation Energy (Ea)

Using the data from Part III, calculate the values listed in the table below for each
measured temperature.

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Kinetics of a Reaction

Measured Measured Average Rate of Reaction, Rate Constant, k, ln k

Temp, K Temp-1, K Time, s M/s (with units)

Graph the data with natural logarithm of the rate constant on the y-axis versus 1/T on the
x-axis. Draw the best linear fit line to determine the slope of the line. The slope of this
line is equal to the quantity –Ea/R, derived from the formula: ln[A]t = -kt + ln[A]0.
Realize this formula fits the generic linear plot y = mx + b. R in this equation should be
represented by 8.314 J/molK. Calculate the activation energy for this reaction. Do not
forget to use proper graphing technique and please indicate the points used to determine
the slope of your curve.

Post-Lab Questions:
1. Why does the reaction rate change as concentrations of the reactants change?
2. Explain the general procedure used to find the rate law.
3. Why does the reaction rate change as a function of temperature?
4. Explain the general procedure used to determine the activation energy?
5. Differentiate between reaction rate and a specific rate constant.
6. Comment on the effect of the catalyst. Predict how the activation energy changes
when a catalyst is added to the reaction.
7. Make a general statement about the consistency of the data as shown by
calculating the orders of reactants, and by the graphical analysis which leads to
activation energy. Were the calculated orders close to integer values? Did the
check of the reaction order give the same value for the order? Were the points of
the graph a straight line?
8. Write a concluding paragraph briefly summarizing your results, discussing
probable sources of error or difficulty and the effects of these errors or difficulties
on your data and/or calculations, and discussing revisions to your technique or
procedure which may alleviate sources of error in future applications of this
experiment.

Gates Chili AP Chemistry 18-13