Chemical April 7

2009
Kinetics Labs
Sukhkaran Dhaliwal
SCH4U
Mr. J. Linzel
Sukhkaran Dhaliwal Chemical Kinetics Labs 2008/2009

Chemical Kinetics Labs

Introduction
Chemical kinetics, also known as reaction kinetics, is the study of rates of chemical processes.
Chemical kinetics includes investigations of how different experimental conditions can influence the
speed of a chemical reaction and yield information about the reaction's mechanism and transition
states, as well as the construction of mathematical models that can describe the characteristics of a
chemical reaction (Pearson, 2004).
The rate of reaction is the change in the amount of reactants or products over a time interval.
The rate of reaction in chemistry, is usually expressed in moles/second (mol/s) or molarity/second
(mol/Ls). There are two ways in which the rate can be expressed: average rate of a reaction or
instantaneous rate of reaction. The average rate of reaction shows how the concentration or molarity
changes over a specific time interval, while the instantaneous rate of reaction shows the rate of change
at a specific time. Differential calculus can often be used when calculating the instantaneous rate of
change. An easier method would be to calculate the slope of the line at the point of tangency.
There are many ways in which chemists can measure reaction rates. Various methods include:
monitoring mass, pH, conductivity, pressure, colour, and volume. When monitoring mass, the mass of
the reactants can be measured over a time interval and if it releases gas, the mass will decrease. In a
reaction involving gasses, the pressure of the system can change as the reaction progresses. An
example would be the decomposition of hydrogen peroxide. As it decomposes in a closed system, the
pressure will increase as oxygen gas is produced. As well as pressure and mass, change in colour can be
used to monitor the progress of a reaction. The absorbance of light is directly related to the
concentration of the compound, so by observing the change in absorbance, the rate of reaction is
monitored.
The speed of a chemical reaction is affected by factors such as the temperature, concentration,
volume, surface area, and orientation. These factors are sufficiently explained through collision theory.
When the temperature is greater, there is a greater fraction of particles that have more energy than the
activation energy, enabling them to collide and react. These particles also have more kinetic energy. By
increasing concentration, while keeping volume and pressure constant, there is a greater chance that
the particles will collide and react. Decreasing the volume is essentially another form of increasing the
concentration. With greater surface area, more collisions can occur; increasing the rate of reaction.
Lastly, orientation is the key for a reaction to occur. If particles do not collide with the correct
orientation, a reaction will not occur. As well, catalysts have the ability to increase the rate of reaction
by lowering the activation energy barrier.

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Generally, the rate of a reaction increases when the concentration of the reactants are
increased. The rate of reaction is directly proportional to the concentration of the reactants. This
relationship can be expressed in a general equation called the rate law equation.

The letters A and B represent the concentration of the reactants. The exponents x and y are
called the rate law exponents (orders of reaction). They do not change with temperature and must be
determined experimentally. Generally, they do not correspond to the stoichiometric coefficients of
their reactants. The letter k represents the proportionality constant called the rate constant. The rate
constant differs for each reaction at any given temperature. The rate constant has different units
depending on what the overall order of the reaction is. The magnitude of the rate constant indicates
the speed of a reaction. Therefore a small rate constant indicates a slow reaction, while a large rate
constant indicates a fast reaction.
The Arrhenius equation is a simple, but remarkably accurate, formula for the temperature
dependence of the rate constant, and therefore, rate of a chemical reaction (IUPAC, 1997). In short, the
Arrhenius equation gives "the dependence of the rate constant k of chemical reactions on the
temperature T (in absolute temperature, such as Kelvin or Rankine) and activation energy as shown
below (IUPAC Goldbook, 1997):

Or

The rate constant is represented by the letter k just like the rate law equation. Ea is activation
energy and has units of Joules. R is the universal gas constant and is equal to 8.314 J K-1 mol-1. The
variable T represents temperature, usually in Kelvin. The variable A represents the frequency factor and
expresses the importance of orientation of the molecules during collisions. The greater the value of A,
the more likely a collision will result in a chemical reaction. The letter e is a mathematical constant
called Eulers number. The modified version of the Arrhenius equation was derived by taking the natural
logarithms of both sides. This equation resembles the equation of a straight line: y = ( m ) ( x ) + b. If lnk
is plotted against T -1, a straight line should result with a slope of -Ea/R and a y-intercept of lnA.
A reaction mechanism is a series of steps that make up an overall reaction. Each step, called an
elementary step, involves a single molecular event, such as a simple collision between atoms, molecules,
or ions. This step cannot be broken down into further, simpler steps. Molecules that are formed in an
elementary reaction and consumed in a subsequent elementary reaction are called reaction
intermediates (Webb, 2002). The term molecularity refers to the number of reactant particles that are
involved in an elementary reaction. They can be either unimolecular (one), bimolecular (two), or
termolecular (three). The molecularity of the slowest step of the reaction mechanism is equal to the
orders of reaction. The slowest step of the reaction mechanism is also called the rate determining step.
This is because a reaction can only be as fast as its slowest step, so it has bearing on the order of
reaction.

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Determining the Rate Expression and Activation Energy

for the Decomposition of Hydrogen Peroxide

Data Collection

Table of Volumes and Concentrations

Trial Volume H2O2 (mL) [H2O2] Before Mixing Volume KI (mL) [KI] Before Mixing
1 4 0.88 1 0.50
2 4 0.88 1 0.25
3 4 0.44 1 0.50
4 4 0.88 1 0.50
Table 1 Table of Volumes and Concentrations for H2O2 and KI

The only values calculated in this table were the concentrations of the H2O2 before mixing.

Table of Temperatures and Initial Rates

Temperature
Trial Reactants Initial Rate (kPa/s)
(C)
1 4 mL 3.0% H2O2 + 1 mL 0.5 M KI 20.10 0.3440

2 4 mL 3.0% H2O2 + 1 mL 0.25 M KI 20.10 0.1744

3 4 mL 1.5% H2O2 + 1 mL 0.5 M KI 20.10 0.0449

4 4 mL 3.0% H2O2 + 1 mL 0.5 M KI 29.90 0.5480

Table 2 Table of Temperatures and Initial Rates

The temperature and initial rate for the reactions were determined using Logger Pro. The temperature
reading was given during the course of the reaction and the initial rate was determined by creating a

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linear fit for the initial increase in kPa and time. From that data, the slope was equal to the initial rate
(kPa/s).

Table of Rates, Concentrations, and Rate Constants

Trial Initial Rate (mol/L s) [H2O2] After Mixing [KI] After Mixing Rate Constant k
1 1.41x10-4 0.704 0.10 4.04x10-3 M-3s-1
2 7.15x10-5 0.704 0.05 4.09x10-3 M-3s-1
3 1.84x10-5 0.352 0.10 4.22x10-3 M-3s-1
4 2.25x10-4 0.704 0.10 6.45x10-3 M-3s-1
Table 3 Table of Rates, Concentrations, and Rate Constants

The initial rate as mol/Ls was calculated by rearranging the ideal gas law. The concentrations of the
reactants were calculated from basic molarity and solution principles. The rate constant (k) was
calculated by first determining the order of the reactants, then using these values with the rate
expression to isolate for k. All full calculations are shown in Data Analysis.

Pressure vs. Time for Trial 1

180
160
140
Pressure (kPa)

120
100
80
60
40
20
0
1 11 21 31 41 51 61 71 81 91 101 111 121 131 141 151 161 171 181 191 201

Time (s)

Figure 1 Pressure vs. Time Graph for Trial 1

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Pressure vs. Time for Trial 2

140

120

100
Pressure (kPa)

80

60

40

20

0
1 11 21 31 41 51 61 71 81 91 101 111 121 131 141 151 161 171 181 191 201

Time (s)

Figure 2 Pressure vs. Time Graph for Trial 2

Pressure vs. Time for Trial 3

112
110
108
106
Pressure (kPa)

104
102
100
98
96
94
92
1 11 21 31 41 51 61 71 81 91 101 111 121 131 141 151 161 171 181 191 201

Time (s)

Figure 3 Pressure vs. Time Graph for Trial 3

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Pressure vs. Time for Trial 4

180
160
140
Pressure (kPa)

120
100
80
60
40
20
0
1 11 21 31 41 51 61 71 81 91 101 111 121 131 141 151 161

Time (s)

Figure 4 Pressure vs. Time Graph for Trial 4

Data Analysis
To calculate the orders of reaction for H2O2 and KI, the method of analyzing initial rates was used. By changing the
concentrations of each, Logger Pro was used to see the change in the rate of reaction (kPa/s), which was eventually converted to
mol/Ls. By comparing how the reaction rates changed to differing concentrations of the reactants, the orders of reaction were
calculated.

Conversion of kPa/s to mol/Ls: Sample Calculation:

Calculating Order of KI: Calculating Order of H2O2:

1.972

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The variable y represents the order of reaction for KI. It can be The variable x represents the order of reaction for H2O2. It can
observed that the value for y is close enough to 1, so therefore be observed that the value for x is close enough to 3, so therefore
rounded to a whole number. rounded to a whole number.

The order of reaction for KI is 1. The order of reaction for H2O2 is 3.

From the above calculations it can be concluded that the rate expression for the catalyzed decomposition of hydrogen peroxide is:

Rate = k[H2O2]3[KI]

To calculate the rate constant k, the orders of reaction first had to be calculated (shown above). After the orders were
calculated, that would mean that there would be only one unknown variable in the rate expression, which would be the rate
constant. By rearranging the rate expression for the catalyzed decomposition of hydrogen peroxide, the rate constant could be
determined for all trials. Since there were three trials at the same temperature, the rate constant will be averaged out, while
the last trial was at a higher temperature, will not be taken into account for the averaging of the rate constant. The
calculations should show that the rate constant for the first three trials is somewhat similar, while the last trial will be different.

Trial 1 Trial 2

Trial 3 Trial 4

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Average of k at 294.25 Kelvin

Now that all the variables and values in the rate law expression have been calculated, it is viable that the activation energy (Ea)
for the reaction be calculated. By using an alternative derivation of the Arrhenius equation, the activation energy can be easily
solved for.

Solving for the activation energy

Rearrange for Ea

The activation energy for the catalyzed decomposition of hydrogen peroxide was 33.79 kJ.

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From the experimental data collected, information such as the order of reaction, value of the
rate constant, rate of reaction, and activation energy could be calculated. The rate expression for the
catalyzed reaction of hydrogen peroxide was:

Rate = k [H2O2]3[KI]
The rate constant, k, was averaged to be 4.22x10-3 M-3s-1 for 293.25 Kelvin. The rate constant
calculated for trials one, two, and three were fairly close to one another showing that experiment was
carried out effectively. As expected, the rate constant increased when the reaction occurred at a higher
temperature. It was calculated to be 6.45x10-3 M-3s-1 for 303.05 Kelvin. This essentially means that more
effective collisions occurred at the higher temperature. With this data, it can be formulated that the
larger the rate constant, the faster the rate of reaction will be.
The order of reaction for the hydrogen peroxide was three and the order of reaction for
potassium iodide was one. The overall order of reaction was four. These values were calculated by
comparing the initial rates of reaction for differing concentrations. After a ratio was set up, the natural
logarithm was taken for both sides to isolate for the unknown value for the order. This was completed
twice: one for the differing concentration of hydrogen peroxide and the other for the differing
concentration of potassium iodide. It was always compared to the base results (trial one).
The following mechanism has been proposed for the catalyzed decomposition of hydrogen
peroxide:
H2O2 + I- IO- H2O

H2O2 + IO- I- + H2O + O2

The first reaction in the mechanism is the rate determining step (slowest reaction). This is quite
easy to determine because the second reactions reactants are H2O2 and IO-. This would mean that
hydrogen peroxide would be the only substance in the rate expression to have an order that is equal to
or greater than one. Since IO- is not a reactant, this would mean that the order of reaction for KI would
be zero, which is not the case. With this being said, the first reaction in the mechanism is indefinitely
the rate determining step because H2O2 and I- are both reactant, which means they have to have an
order equal to or greater than one.
The activation energy for the catalyzed decomposition was calculated to be 33.79 kJ. A modified
version of the Arrhenius equation was used to calculate the activation energy. If the hydrogen peroxide
was to decompose without the presence of a catalyst, the activation energy would have been higher,
but with potassium iodide acting as the catalyst in the reaction; it was able to lower the activation
energy barrier.

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Determining the Rate and Order of a

reaction Using colorimetry
Data Collection

Table of Reactants, Concentrations, and Initial Rates

[FeCl3] After [KI] After
Trial Reactants Initial Rate (s-1)
Mixing Mixing
1 1.5 mL 0.0500 M FeCl3 + 1.5 mL 0.0500 M KI 0.0250 0.0250 0.163

2 1.5 mL 0.0500 M FeCl3 + 1.5 mL 0.0250 M KI 0.0250 0.0125 0.040

3 1.5 mL 0.0250 M FeCl3 + 1.5 mL 0.0500 M KI 0.0125 0.0250 0.083

Table 1 Table of Reactants, Concentrations, and Initial Rates

The only values calculated in this table were the concentrations of iron (III) and potassium iodide after
mixing. Basic molarity and solutions chemistry was used to determine the values. The initial rate was
determined from the graphs obtained from Logger Pro. The values represent the initial rate of change
(slope) of the graphs.

Absorbance vs. Time for Trial 1

1.8
1.6
1.4
Absorbance

1.2
1
0.8
0.6
0.4
0.2
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

Time (s)

Figure 1 Absorbance vs. Time Graph for Trial 1

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Absorbance vs. Time for Trial 2

1.2

1
Absorbance

0.8

0.6

0.4

0.2

0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

Time (s)

Figure 2 Absorbance vs. Time Graph for Trial 2

Absorbance vs. Time for Trial 3

1.2

1
Absorbance

0.8

0.6

0.4

0.2

0
0 5 10 15 20 25 30 35 40 45

Time (s)
Figure 3 Absorbance vs. Time Graph for Trial 3

Data Analysis
To calculate the orders of reaction for FeCl3 and KI, the method of analyzing initial rates was used. By changing the
concentrations of each, Logger Pro was used to see the change in the rate of reaction (s-1). A colorimeter was used to measure
absorbance, which is defined as a logarithmic measure of the amount of light that is absorbed when passing through a substance.
It does not have any units. By comparing how the reaction rates changed to changing the concentrations of the reactants, the
orders of reaction were calculated.

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Before calculating the orders of reaction, the concentrations of iron (III) chloride and potassium iodide were calculated. It cannot
be done in one step, but rather requires two sets of calculations. To calculate the concentration of iron (III) chloride, the
dilution was treated as if potassium iodide was water. To calculate the concentration of potassium iodide, the dilution was
treated as if iron (III) chloride was water.

[FeCl3] Calculation Trial 1 [KI] Calculation Trial 1

[FeCl3] Calculation Trial 2 [KI] Calculation Trial 2

[FeCl3] Calculation Trial 3 [KI] Calculation Trial 3

Calculating Order of FeCl3: Calculating Order of KI:

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The variable y represents the order of reaction for KI. It can be The variable y represents the order of reaction for KI. It can be
observed that the value for y is close enough to 1, so therefore observed that the value for y is close enough to 2, so therefore
rounded to a whole number. rounded to a whole number.

The order of reaction for FeCl3 is 1. The order of reaction for KI is 2.

The data collected from the colorimeter, which measured the absorbance of the solution, was
used to calculate the order of reaction for iron (III) chloride and potassium iodide. The rate expression
for the reaction is as follows:

Rate = k [FeCl3][KI]2
The order of reaction for iron (III) chloride was one and the order of reaction for potassium
iodide was two. The overall order of reaction was three. Though the rate of reaction did not have units
of mol/Ls, the order could still be calculated. To calculate the order, it wouldnt have mattered if the
units were mol/Ls or s-1 because the ratio between the two rates being compared would still be the
same after it was converted (if it could have been converted).
It was impossible to calculate the rate constant, k, for obvious reasons. Though the rate was in
-1
s , this could not have been used to determine the rate constant. The rate of reaction would have to be
in mol/Ls, otherwise the rate constant would have incorrect units and values. To calculate the rate
constant, another experiment would have to be conducted using Beers Law. This experiment would
then allow the conversion from absorbance to a specific molar concentration. With the data from this
experiment, calculating the rate constant would be possible. It is not possible with either the rate
expression or the Arrhenius equation.

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