Iodine Clock Reaction Experiment Five

Chemical Kinetics: Iodine Clock Reaction

In the previous experiment, we discussed the factors that influence the rate of a
chemical reaction and presented the terminology used in quantitative relations in studies
of the kinetics of chemical reactions. That material is also pertinent to this experiment
and should be studied before you proceed further.

This experiment involves the study of the rate properties, or chemical kinetics, of
the following reaction between iodide ion and bromate ion under acidic conditions:

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

This reaction proceeds at an easily measurable rate that depends on the

concentrations of the I-, BrO3-, and H+ ions according to the rate law discussed in the
previous experiment. For this reaction, the rate law takes the form

rate = k [I-]m [BrO3-]n [H+]p (2)

One of the main purposes of the experiment will be to evaluate the rate constant, k, and
the reaction orders m, n and p for this reaction. We will also investigate the manner in
which the reaction rate depends on temperature and will evaluate the activation energy,
Ea, for the reaction.

Our method for measuring the rate of the reaction involves what is frequently
called a "clock" reaction. In addition to Reaction 1, whose kinetics we will study, the
following reaction will also be made to occur simultaneously in the reaction flask:

I2(aq) + 2 S2O32-(aq) → 2 I-(aq) + S4O62-(aq)

As compared with (1) this reaction is essentially instantaneous. The I2 produced in (1)
reacts completely with the thiosulfate, S2O32-, ion present in the solution so that once all
the thiosulfate ion has reacted, the concentration of I2 is effectively zero. As soon as the
S2O32- is gone from the system, the I2 produced by (1) remains in the solution, and its
concentration begins to increase. The presence of I2 is made strikingly apparent by a
starch indicator which is added to the reaction mixture, since I2 even in small
concentrations reacts with starch solution to produce a blue color.

By carrying out Reaction 1 in the presence of S2O32- and a starch indicator, we

introduce a "clock" into the system. Our clock tells us when a given amount of BrO3- ion
has reacted (1/6 mole BrO3- per mole S2O32-), which is just what we need to know since
the rate of reaction can be expressed in terms of the time it takes for a particular amount
of BrO3- to be used up. In all our reactions, the amount of reactants that react in the time

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 Iodine Clock Reaction Experiment Five

we measure will be constant and small as compared to the initial amounts of those
reactants. This means that the concentrations of all reactants will be essentially constant
in Equation 2, and hence so will the rate during each reaction.

In our experiment, we will carry out the reaction between BrO3-, I-, and H+ ions
under different concentration conditions. Measured amounts of each of these ions in
water solution will be mixed in the presence of a constant small amount of S2O32-. The
time it takes for each mixture to turn blue will be measured. The time obtained for each
reaction will be inversely proportional to its rate. By changing the concentration of one
reactant and keeping the other concentrations constant, we can investigate how the rate
of the reaction varies with the concentration of a particular reactant. Once we know the
order for each reactant, we can determine the rate constant for the reaction.

In the last part of the experiment we will investigate how the rate of the reaction
depends on temperature. You will recall that in general the rate increases sharply with
temperature. By measuring how the rate varies with temperature we can determine the
activation energy, Ea, for the reaction by making use of the Arrhenius equation:

ln k = -Ea/RT + constant (3)

In this equation, k is the rate constant at the Kelvin temperature T, Ea is the activation
energy, and R is the gas constant. By plotting ln(k) against 1/T we should obtain, by
Equation 3, a straight line whose slope equals -Ea/R. From the slope of that line, we can
easily calculate the activation energy.

Procedure

Dependence of Reaction Rate on Concentration

In the following table, we have summarized the reagent volumes to be used in

carrying out the several reactions whose rates we need to know in order to find the
general rate law for Reaction 1.

Reaction Mixtures at Room Temperature (in mL)

Reaction Reaction Flask I

Mixture 0.010 M KI 0.001 M Na2S2O3 H2O
1 5.0 5.0 5.0
2 10.0 5.0 0
3 5.0 5.0 0
4 5.0 5.0 0
5 4.0 5.0 6.0

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 Iodine Clock Reaction Experiment Five

Reaction Reaction Flask II

Mixture 0.040 M KBrO3 0.10 M HCl
1 5.0 5.0
2 5.0 5.0
3 10.0 5.0
4 5.0 10.0
5 2.0 8.0

Since there are several reagents to mix and we don't want the reaction to start
until we are ready, we will put some of the reagents into one flask and the rest into
another, selecting them so that no reaction occurs until the contents of the two flasks are
mixed. For reaction mixture 1, measure out 5.0 mL 0.010 M KI, 5.0 mL 0.001 M
Na2S2O3, and 5.0 mL distilled water into a 125-mL Erlenmeyer flask (Reaction Flask I).
Into a second 125-mL Erlenmeyer flask, measure out 5.0 mL 0.040 M KBrO3, 5.0 mL
0.10 M HCl, and add 3 or 4 drops of starch indicator solution (Reaction Flask II).

Pour the contents of Reaction Flask II into Reaction Flask I and swirl the
solutions to mix them thoroughly. Note the time at which the solutions were mixed.
Continue swirling the solution. It should turn blue in about 2 minutes. Note and record
the time at the instant that a blue color appears. Record the temperature of the blue
solution to 0.2 oC.

Repeat the procedure with the other mixtures. Don't forget to add the indicator
before mixing the solutions in the two flasks. The reaction flasks should be rinsed with
distilled water and dried between runs. The temperature should remain about the same
for all the runs. Repeat any experiments that did not appear to proceed properly.

Dependence of Reaction Rate on Temperature

In this part of the experiment, the reaction will be carried out at several different
temperatures using Reaction Mixture 2 in all cases. The temperatures we will use will be
about 20 oC (which you have already done), 40 oC, 10 oC and 0 oC.

Use your Mixture 2 data for the time and temperature values in the 20 oC column
of table 2. To determine the time at 40 oC proceed as follows. Make up Reaction
Mixture 2 as you did in Part A, including the indicator. However, instead of mixing the
solutions in the two flasks at room temperature, place the flasks into water at 40 oC
drawn from the hot water tap into a plastic tub. Check to see that the water is indeed at
about 40 oC, and leave the flasks in the water for several minutes to bring them to the
proper temperature. Then mix the two solutions, noting the time of mixing. Continue
swirling the reaction flask in the warm water. When the color change occurs, note the
time and the temperature of the solution in the flask.

Repeat the experiment at about 10 oC, cooling all the reactants in water at that
temperature before starting the reaction. Record the time required for the color to change
and the final temperature of the reaction mixture. Repeat once again at about 0 oC, this

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 Iodine Clock Reaction Experiment Five

time using an ice-water bath to cool the reactants.

Dependence of the Reaction Rate on the Presence of Catalyst

Some ions have a pronounced catalytic effect on the rates of many reactions in
water solution. Observe the effect on this reaction by once again making up Reaction
Mixture 2. Before mixing, add 1 drop 0.5 M [NH4]2MoO4, ammonium molybdate, and a
few drops of starch indicator to Reaction Flask II. Swirl the flask to mix the catalyst
thoroughly. Then mix the solutions, noting the time required for the color to change.
Record this time in the data section.

Data and Calculations

Orders of the Reaction. Rate Constant Determination

For the reaction:

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

we have the rate law and reaction rate given by:

rate = k [I-]m [BrO3-]n [H+]p = - ∆[BrO3-] (4)

∆t

In all the reaction mixtures used in the experiment, the color change occurred when a
constant predetermined number of moles of BrO3- had been used up by the reaction. The
color "clock" allows you to measure the time required for this fixed number of moles of
BrO3- to react. The rate of each reaction is determined by the time required for the color
to change, since in Equation 4 the change in concentration is inversely proportional to the
time, t. We are mainly concerned with relative rather than absolute rate; therefore, we
will take all relative rates as being equal to 1000/t. Fill in the table on the next page, first
calculating the relative reaction rate for each mixture.

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 Iodine Clock Reaction Experiment Five

Table 1
Time t(sec) Relative rate Reactant concentrations Temp
Reaction for color of reaction, in reacting mixture (M) in oC
mixture to change 1000/t [I-] [BrO3-] [H+]

1 ___________ _____________ 0.0020 _________ ________ ________

2 ___________ _____________ _________ ________ ________

3 ___________ _____________ _________ ________ ________

4 ___________ _____________ _________ ________ ________

5 ___________ _____________ _________ ________ ________

The reactant concentrations in the reaction mixture are not those of the stock solutions,
since the reagents were diluted by the other solutions. The final volume of the reaction
mixture is 25 mL in all cases. Since the number of moles of reactant does not change on
dilution we can calculate the concentrations of all reactants in the table above.

Determination of the Orders of the Reaction

Given the data in the table, the problem is to find the order for each reactant and
the rate constant for the reaction. Since we are dealing with relative rates, we can modify
Equation 2 to read as follows:

relative rate = k' [I-]m [BrO3-]n [H+]p (5)

We need to determine the relative rate constant k' and the orders m, n and p in such a way
as to be consistent with the data in the table.

The solution to this problem is quite simple once you make a few observations on
the reaction mixtures. Each mixture (2 to 4) differs from Reaction Mixture 1 in the
concentration of only one species (see table). This means that for any pair of mixtures
that includes reaction Mixture 1, there is only one concentration that changes. We can
then find the order for the reactant whose concentration was changed.

Write Equation 5 below for Reaction Mixtures 1 and 2, substituting the relative
rates and the concentrations of I-, BrO3-, and H+ ions from the table you have just
completed.

Relative rate 1 = ______________ = k [ ]m [ ]n [ ]p

Relative rate 2 = ______________ = k [ ]m [ ]n [ ]p

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 Iodine Clock Reaction Experiment Five

Solve for m, the order of the reaction with respect to the I- ion, to two decimal places and
then round off to the nearest integer.

m = ___________ (2 decimal places) m = __________ (nearest integer)

Apply the same approach to find the value of n, the order of the reaction with respect to
the BrO3- ion. Show your set-up.

n = ___________ (2 decimal places) n = __________ (nearest integer)

Apply the method once again to find p, the order with respect to the H+ ion. Show your
set-up.

p = ___________ (2 decimal places) p = __________ (nearest integer)

Therefore, the rate law is written as rate = __________________________________

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 Iodine Clock Reaction Experiment Five

Determination of the Value of Relative Rate Constant

Having found m, n, and p (nearest integers), the relative rate constant, k' can be
calculated by substitution of m, n, p and the known rates and reactant concentrations into
Equation 5. Calculate k for Reaction Mixtures 1 to 4 and then determine the average
value.

Reaction 1 2 3 4

k ________ ________ _________ ________ kave________

Calculations for each k value:

Briefly explain why k should have nearly the same value for each of the reactions.

Determination of Relative Rate and Reaction Time for Mixture 5

For Reaction Mixture 5, use kave and the appropriate concentrations from table 1 in
Equation 5 to predict (calculate) the relative rate. Then use this value to predict
(calculate) the reaction time, t, for Mixture 5. Show your calculations below.

relative ratepredicted________ tpredicted________ tobserved________

Calculate the percent difference of your reaction times.

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 Iodine Clock Reaction Experiment Five

The Effect of Temperature on Reaction Rate: The Activation Energy

To find the activation energy for the reaction, it will be helpful to complete the
table below using Mixture 2. Since the reactions at the different temperatures all involve
the same reactant concentrations, the rate constants, k, for two different mixtures will
have the same ratio as the reaction rates themselves for the two mixtures. This means
that in the calculation of Ea, we can use the observed relative rates instead of rate
constants. Record the reaction times and temperatures in table 2. Proceeding as before,
calculate the relative rates of reaction for each of the mixtures and enter values in (c).
Then complete the rest of the table.

Table 2 – Data for Mixture 2 Approximate temperature in oC

20o 40o 10o 0o

(a) Time in seconds

for color to appear ______ ______ ______ ______

(b) Actual temperature of

reaction mixture ______ ______ ______ ______

(c) Relative rate = 1000/t ______ ______ ______ ______

(d) ln of relative rate ______ ______ ______ ______

(e) temperature T in K ______ ______ ______ ______

(f) 1/T ______ ______ ______ ______

Use the appropriate values from table 2 and plot ln(relative rate) vs 1/T. Find the slope
of the line obtained by drawing the best-fitting line through the experimental points.
Make certain to include your Arrhenius plot with this report. Show your calculations
below.

Slope = ________________

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 Iodine Clock Reaction Experiment Five

The slope of the line equals -Ea/R, where R = 8.314 Joules/(mole K). Use this
relationship to calculate the activation energy, Ea, for your reaction.

Ea = _________________ kJ/mol

The Effect of a Catalyst on Reaction Rate

Catalyzed
Reaction 2 Reaction 2

Time for color to appear (sec) __________ __________

Would you expect the activation energy, Ea, for the catalyzed reaction to be greater than,
less than, or equal to the activation energy for the uncatalyzed reaction? Briefly explain.

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 Iodine Clock Reaction Experiment Five

Advance Study Assignment: Iodine Clock Reaction

1. A student studied the clock reaction described in this experiment. She set up a
reaction mixture by mixing 10.0 mL of 0.010 M KI, 10.0 mL of 0.0010 M
Na2S2O3, 20.0 mL of 0.040 M KBrO3 and 10.0 mL of 0.10 M HCl using the
procedure given. It took 40.0 seconds for the color to turn blue.

a. She found the concentration of each reactant in the reacting mixture by

realizing that the number of moles of each reactant did not change when
that reactant was mixed with the others, but that its concentration did.
The volume of the mixture was 50.0 mL. Find the concentration of each
reactant.

[I-] = __________M; [BrO3-] = __________M; [H+] = __________M

. b. What is the relative rate of the reaction (1000/t)?

____________________

2. The student repeated the experiment using reaction mixture 1 by mixing 10 mL of

0.010 M KI, 10 mL of 0.0010 M Na2S2O3, 10 mL of 0.040 M KBrO3, 10 mL of
0.10 M HCl and 10 mL of H2O. It took 75 seconds to turn blue.

Find the concentration of each reactant after mixing:

[I-] = ________M; [BrO3-] = _______M; [H+] = _______M

What is the relative rate of the reaction (1000/t)?

____________________

3. Use the information above to determine the order with respect to BrO3-.

n = _________(2 decimal places) n = _________(nearest integer)

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