LABORATORY SESSION 2

REACTION KINETICS. METHOD OF INITIAL RATES

1. OBJECTIVE

Study the kinetics of chemical reactions and the factors that influence it.

Specific Objectives:
• Determine the rate law for a chemical reaction. The effect of the concentrations
in the rate will be analyzed.
• Determine the activation energy for a chemical reaction. The effect of the
temperature in the reaction rate will be studied.

2. THEORETICAL BASIS

The purpose of this experiment is to characterize the reaction between iodide, I-,
peroxydisulfate (or persulfate), S2O82-, and thiosulfate, S2O32-. This reaction system is an
example of what is commonly known as a “clock reaction.” At one step during the
reaction, a product is made which reacts with an indicator solution; the resulting change
in color is used to time the reaction.

In this experiment we will study the kinetics of the reaction between iodide ions
(I ) and persulphate ions (S2O82-) in aqueous medium. The reaction to be studied in this
-

experiment is represented by the following balanced chemical equation:

MAIN REACTION (Reaction I)

2 I- (aq) + S2O82- (aq) → I2 (aq) + 2 SO42- (I)

To study a reaction kinetically we must determine the reaction’s rate. One

approach is to measure the time required to react a known amount of reactant or the time
required to make a known amount of product.

Reaction rate can be obtained observing how concentrations of some of reactants

or products vary over time, as expressed by the following relations:

1 𝑑[𝐼 − ] 𝑑[𝑆2 𝑂82− ] 𝑑[𝐼2 ] 1 𝑑[𝑆𝑂42− ]

𝑅𝑎𝑡𝑒 = − = − = = (1)
2 𝑑𝑡 𝑑𝑡 𝑑𝑡 2 𝑑𝑡

We will choose the variation of the concentration of persulphate to track the

reaction. Therefore, the reaction rate will be defined according to the expression:
𝑑[𝑆2 𝑂82− ]
𝑅𝑎𝑡𝑒 = − (2)
𝑑𝑡
Chemistry – Laboratory Practices
Laboratory session 1: Acid-Base.

On the other hand, it is possible to write a general equation for the rate law as
follows:
𝑟 = 𝑘 × [𝐼 − ]𝑚 × [𝑆2 𝑂82− ]𝑛 (3)

where k is the kinetic constant, which depends on the temperature, and m and n are the
partial reaction orders of iodide (I-) and persulphate (S2O82-) ions respectively. To fully
determine the kinetic equation is therefore necessary to obtain experimentally the partial
orders of the reaction (m, n) as well as the value of k.

A simple method to get the value of m and n is the so-called the method of the
initial rates which consists of measuring the time needed to consume a very small amount
of reactants, so small that you can assume that their concentrations remain constant and
equal to the initial ones. In this way the variation of concentration over time can be
considered as the reaction rate at time virtually zero, i.e. the initial rate. In this respect, to
obtain m, reaction rates could be measured varying the initial concentration of I- keeping
constant S2O82-; whereas to obtain n you should vary the S2O82- concentration keeping
constant I-. Under these experimental conditions, time variation is also small and the
initial rate can be calculated as:
-
Δ [S2 O82 ]
r = r0 = - (1)
Δt
Considering the initial time is zero, t = t, and then

-
Δ [S2 O82 ]
r = r0 = - (2)
t

The elapsed time until a small amount of S2O82- is consumed will be measured
through using what is known as a “clock reaction” to alert us when the fixed amount of
persulphate (S2O82-) has been consumed. A second reaction (REACTION II, not the one
we are studying) will be run in our reaction flask along with Reaction I. REACTION II
is many times faster than Reaction I.

Thus, all the I2 produced in Reaction I will immediately be converted to I– by

Reaction II until all of the S2O32– has been consumed. At that point, the I2 begins to
accumulate in the solution.

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MAIN REACTION (Reaction I)

2 I- (aq) + S2O82- (aq) → I2 (aq) + 2 SO42- (I)

SECONDARY REACTION (Reaction II, very fast reaction)

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

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

I2 (aq) + STARCH → COLOURED COMPLEX (III)

A starch indicator is included in the reaction mixture. This indicator forms a deep
blue or brownish complex in the presence of I2. All the other chemical species used in
this experiment are colorless. Thus, a dramatic color change from colorless to blue is
observed at the instant when all the S2O32-has been consumed. You will measure the
time it takes for this color change to occur. This is Δt, the denominator in the reaction
rate.

According to this, we consider that all the iodine of the first reaction (I) is quickly
consumed while thiosulphate (S2O32-) is present. When it is exhausted (all the S2O32- is
consumed), the free molecular iodine (I2) can be detected with the presence of starch in
the solution. Molecular iodine (I2) dyes blue the starch (if the solution of iodine is not
saturated the color could be brown).

From the stoichiometry of the reactions (I) and (II) you can write the following
stoichiometric relations:

n(S2O82) <> n(I2) <> 2 n(S2O32-)

i.e. each mole of persulphate S 2 O 8 2 - consumed in the reaction (I) produces a mole of
molecular iodine which in turn would consume, according to the consecutive reaction
(II), two moles of thiosulfate (S2O32-). This stoichiometric analysis results in the following
relation:
1
- Δ[S2 O82-] = - Δ[S2 O32-] (3)
2
and consequently, the reaction rate would be written as

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Chemistry – Laboratory Practices
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Δ[S2 O82-] 1 Δ[S2 O32-]

Rate = - =- (4)
t 2 t
Issues as far described lead to the conclusion that if we use the same initial
thiosulphate concentration and different concentrations of iodide and persulphate in
different experiments, we will get the partial orders of reaction. If you use a small
concentration of thiosulfate e.g. [S2O32-] = 10-3 M, the concentrations of initial reactants
will hardly change during the reaction. We can therefore say that during the time
thiosulfate is consumed, reactant concentrations remain almost constant and then:
[S2 O82-]  [S2 O82- ]0 [I-]  [I- ]0 (5)

where [S2O82-]0 and [I-]0 are the initial concentrations of persulphate and iodide,
respectively.

Determination of the Activation Energy of a Reaction

The kinetic constant of a process is dependent upon the temperature and is given
by the so-named Arrhenius equation
Ea
−
k = Α ·e RT
(6)
where  is the frequency factor –characteristic of the process- Ea is the activation
energy, R is the constant of ideal gases 8.31441 J·K-1·mol-1, and T is the absolute
temperature.

Taking natural logarithms in equation (9)

Ea
ln k = ln Α − (7)
R·T
Therefore, plotting the inverse of the absolute temperature versus ln K , we should
obtain a straight line with a slope of –Ea/R.

Note that this equation is that of a straight line with the form y = a + b· x where:

y = ln k ; x = 1/T; a = ln A and b = –Ea/R

If k is measured at several temperatures and ln k is plotted vs. 1/T, the slope and
y intercept of the resulting line will allow the values of Ea and A for the reaction can be
found. Ea is expressed in units of kJ/mole or kcal/mole and A in the same units as the rate
constant, k.

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3. EXPERIMENTAL PART

a) Materials and Reagents

• 150 mL KI 0.2 M

• 50 mL KCl 0.2M

• 150 mL (NH4)2SO4 0.1 M

• 100 mL Na2S2O3 5·10-3 M

• 100 mL (NH4)2S2O8 0.1 M

• 10 mL of starch

• Pasteur pipette (one piece)

• 10 mL pipettes and propipettes (5 units)

• Thermostatic baths

• 5 tests tubes

• 50 mL enrlenmeyer

• Chronometer

• Metallic Grid

b) Procedure

The following reactant solutions will be already prepared for this experiment:

150 ml. KI 0.2 M

100 ml. (NH4)2S2O8 0.1 M

50 ml. KCl 0.2 M

150 ml. (NH4)2SO4 0.1 M.

100 ml. Na2S2O3 5·10-3 M

10 ml. of starch

To carry out the method of the initial rates you will perform five tests at constant
temperature. The necessary amounts for each experiment are shown in Table 1. To dilute
the initial concentrations of reactants, use aqueous solutions of KCl and (NH4)2SO4, instead
of water for keeping constant the saline concentration in all cases (since the reaction rate
may vary with ion concentration).

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a) Test tubes must be labeled as 1, 2, 3, 4 and 5.

b) In each of the test tubes add the corresponding aliquot of ammonium

persulphate.

c) For each test, pour with the corresponding pipette in the 50 mL Erlenmeyer
the volumes of KI, KCl, Na2S2O3, (NH4)2SO4 and the drops of starch that are indicated in
Table 1.

d) For each test, empty the content of the test tube in the Erlenmeyer shaking
its content to homogenize the mixture, and, at the same time, start the chronometer.

e) Stop the chronometer at the moment the reaction mixture starts changing
color and note down the elapsed time in the corresponding table (Table 2, Table 3 or Table
4).

Table 1. - Quantities of reactant for each test (in milliliters)

Erlenmeyer Test tube

Test KI KCl Na2S2O3 Starch (NH4)2S2O8 (NH4)2SO4

(0.2M) (0.2M) (0.005M) (0.1M) (0.1M)

1 10 - 5 10 -

2 5 5 5 10 -
2 or 3
3 10 - 5 5 5
drops
4 10 - 5 2.5 7.5

5 4 6 5 10 -

The tests will be carried out at room temperature (25ºC), and at two other higher
temperatures; in the latter two cases, reactants must be thermostated (at least 5 minutes
before starting the reaction) introducing the Erlenmeyer and the test tubes in a
thermostatic bath at the temperature the experiment is going to be carried out.

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5 6 5 6
4 7 4 7

8 8
3 3

2 9 2 9

1 10
1 11

c) Calculations
• Initial concentrations of reactants and the reaction rate of each test must be calculated.
Write down all the initial concentrations of iodide I- and persulphate S 2 O 8 2 - ions in
tables 2, 3 and 4 .

• Calculate the initial rate for each of the five tests carried out at constant temperature.
Since:
-
Δ [S2 O82 ]
r = r0 = -
Δt
Considering the initial time is zero, t = t, and then
-
Δ [S2 O82 ]
r = r0 = -
t
Given that:
1 1 5·10 -3 M * 5 ml Na 2 SO 3
-  [ S 2O 82- ] = [ S 2O 32- ] =  = 5· 10 -4 M
2 2 25 ml total
We can calculate the initial rate for each experiment (test 1-5) using the following
equation:
5·10 −4 M
Rate0 =
t

• Obtaining partial orders m and n: Reaction orders are obtained comparing the rate
equations of the experiments where the same initial concentration of reactants is used.

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[I-] (Experiment 1) = [I-] (Experiment 3) = [I-] (Experiment 4)

[S2O82-] (Experiment 1) = [S2O82-] (Experiment 2) = [S2O82-] (Experiment 5)

[S2O82-] = constant  Experiments 1, 2 and 5:

r = k· [I- ]m·[S2 O82 ]n

-

If [S2O82-] = constant, the rate equation can be written as:

r = k· [S2 O82 ]n·[I- ]m = k'·[I- ]m

-

where k' = k· [S2 O82 ]n

-

Taking natural logarithms to this equation we will obtain:

ln r = ln k’ + m ln [I-]

Note that this equation is that of a straight line with the form:

y = a + b· x

where:

y = ln r ; x = ln [I-]; a = ln k’ and b = m

Taking the reaction rates and the concentrations of iodine for the experiments 1,
2 and 5, and representing Ln r versus Ln[I-] for these experiments, we will obtain a
straight line whose slope is the value of m.

[I-] = constant  Experiments 1, 3 and 4:

r = k· [I- ]m·[S2 O82 ]n

-

If [I-] = constant, the rate equation can be written as:

r = k· [S2 O82 ]n·[I- ]m = k' '·[S2 O82 ]n

- -

where k' ' = k· [I - ]m

Taking natural logarithms to this equation we will obtain:

ln r = ln k’’ + n ln [S2O82-]

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Chemistry – Laboratory Practices
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Note that this equation is that of a straight line with the form:

y = a + b· x

where:

y = ln r ; x = ln [S2O82-]; a = ln k’’ and b = n

Taking the reaction rates and the concentrations of iodine for the experiments 1,
2 and 5, and representing Ln r versus ln [S2O82-] for these experiments, we will obtain a
straight line whose slope is the value of n.

• Calculation of the kinetic constant:

Once the partial orders have been determined and using all the calculated rate
constants from all the five experiments performed at the same temperature, an average
rate constant, <k>, for each temperature can be calculated. Five rate constants will be
calculated.
𝑟0
𝑘= −𝑚
[𝐼 ] · [𝑆2 𝑂82− ]𝑛

An average kinetic constant will be obtained for each temperature with the kinetic
constant of each experiment.

• Determination of the activation energy:

Through the use of these average constants, activation energy will be calculated
using the Arrhenius equation:
Ea
ln k = ln Α − (8)
R·T
Plotting the inverse of the absolute temperature versus ln K , we should obtain a
straight line with a slope of –Ea/R. Note that this equation is that of a straight line with
the form y = a + b· x where:

y = ln k ; x = 1/T; a = ln A and b = - Ea/R

Activation energy can be calculated from the slope.

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LABORATORY SESSION 2 – REACTION KINETICS. METHOD OF INITIAL
RATES

1. Fill in the following table with the results obtained in the experiment.

Table 1. - Rates and rate constants at 25 ºC

[S2O82-] k
T (ºC) Test [I-] (M) t (s) v (M s-1)
(M) (Units)
25 1
25 2
25 3
25 4
25 5
<k> at 25 ºC

Table 2. - Rates and rate constants at T1 > 25 ºC

[S2O82-] k
T (ºC) Test [I-] (M) t (s) v (M s-1)
(M) (Units)
1
2
3
4
5
<k> at T1

Table 3. - Rates and rate constants at T2 > T1

[S2O82-] k
T (ºC) Test [I-] (M) t (s) v (M s-1)
(M) (Units)
1
2
3
4
5
<k> at T2
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2. Calculate the partial orders of the reaction for each of the temperatures under study
making the following plots:
• 𝐥𝐧 𝝂 = 𝐥𝐧 𝒌`` + 𝒎 𝐥𝐧[𝑰− ]
• 𝐥𝐧 𝝂 = 𝐥𝐧 𝒌` + 𝒏 𝐥𝐧[𝑺𝟐 𝑶𝟐− 𝟖 ]

3. Using the average values of the kinetic constant determined for each temperature (25
ºC, T1, and T2) estimate the activation energy of the reaction by plotting:
𝑬𝒂 𝟏
𝐥𝐧 𝒌 = 𝐥𝐧 𝑨 − 𝑹 𝑻

Questions

1. Is bimolecular the studied reaction? Support your answer

2. Why the initial rate method is used in this experiment? Suggest some other
experimental methods for studying the kinetics of a reaction.

3.- Deduce which are the units of the rate constant.

4.- Reason out why it is preferable to obtain the activation energy from the slope of a
straight line when plotting Ln<k > vs. 1/T instead of using the expression:

k 2 Ea 1 1 
Ln =  − 
k1 R  T1 T2 

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