CHEMICAL KINETICS

CH3511 EXPERIMENT (REV’D 3/25/06)

INTRODUCTION

A fiber optic spectrometer will be used to find the values for the rate constant and the order of the
reaction shown in equation 1 and described by the rate law shown in equation 2. You will also
determine the activation energy of the reaction by studying the effects of temperature on the rate
constant.

2I − + S 2 O 28− → I2 + 2SO 24− (1)

d [ I2 ]
rate = = k [ I − ] α [S 2 O 28 − ] β (2)
dt

Here k is the rate constant and α and β are the orders of iodide and persulfate, respectively.

The iodine formed in the reaction will combine with the iodide according to the following equilibrium
reaction to form the triiodide ion.

I2 + I− ↔ I3− (3)

The equilibrium constant for this reaction at 298 Kelvin is 697. Consequently, we will assume that
all of the iodine formed in equation 1 will become triiodide ion. You can then use the UV
absorption of triiodide ion at roughly 300 and 350nm to follow the appearance of the iodine using
equation 4:

A
[ I 2 ] ≈ [ I 31− ] = ( 4)
εl

Here is the molar absorptivity constant, l represents the path length of the spectrometer (1cm for
many spectrometers) and A is the absorbance of the triiodide ion. Equation 2 can then be
rearranged to give equation 5.

A
d
rate =
εl
dt
[ ] [S O ]
= k I1−
α
2
2− β
8 (5)

The orders of the reaction, α and β, may be determined mathematically by using a logarithmic
form of equation 5:
 ln(rate ) = ln k + α ln[I1− ] + β ln[S 2 O 82− ] ( 6)

This is accomplished experimentally by holding the initial concentration of one of the reactants
constant and varying the concentration of the other and then reversing the process for the other
reactant. A linear regression can than be used to obtain the value for the respective orders of each
of the reactants. For example, α can be evaluated by measuring the initial rates of reaction where
the persulfate ion is kept constant and the iodide ion is changed by finding the slope of a linear
regression analysis using equation 7:

ln(rate) = k ' + α ln[I − ] (7)

Where k’ = lnk + βln[S2O82-]

Once α and β have been determined, k can be evaluated using each of the measured rates and
equation 2.

The reaction constant is dependent upon ionic strength and it will therefore be necessary to keep
the ionic strength constant by using appropriate amounts of aqueous sodium chloride. The
equation for calculating ionic strength is shown in equation 9.

1 2
I = Mi z i ( 9)
2 i

Where Mi is the concentration (in molarity) of the ith species, and zi is the charge. For this
experiment, the auto-ionization of water can be neglected.

Rate constants also depend strongly on temperature. This temperature dependence fits the
Arrhenius equation for many reactions:

Ea
−
k = Ae RT
(10)

Where A is the Arrhenius constant that is characteristic of the reaction, Ea is the activation energy,
and R is the gas constant.

Taking the log of equation 10 gives us the following:

Ea
ln k = ln A − (11)
RT

Thus, a plot of lnk versus 1/T is a straight line that allows us to obtain Ea from the slope and A from
the intercept.
PRE LABORATORY EXERCISES

1. Calculate the ionic strengths of the sample reactions solutions described in table 1 of the
Laboratory Exercise.

2. Calculate the amount of grams to prepare 500mL of each of the solutions needed for the
experiment (listed in Table 1, below).

3. Read through the Laboratory Exercise below. A constant temperature bath is used to control
the temperature since the rate constant depends on temperature. When placing test solutions
in the water bath to reach thermal equilibrium, should they contain the appropriate amounts of
all four solutions (KI, K2S2O8, and 2 NaCl) or should the final mixing be performed AFTER
thermal equilibrium is reached? Please explain.

4. Initially, the iodide and persulfate ions react at a linear rate until chemical equilibrium is
approached (the rate slows down). From this observation, how will you obtain the INITIAL
rates of reaction for use in equation (7) and subsequent calculations?

5. Why is it important to use the initial rates of reaction in all calculations?

LABORATORY EXERCISE

Table 1: Table of Concentrations

KI NaCl K2S2O8 NaCl H2O

0.05M 0.05M 0.025M 0.075M
10mL 0mL 10mL 0mL 10mL
Find α 8mL 2mL
(Hold (Hold (Hold
6mL 4mL Constant) Constant) Constant)
4mL 6mL
2mL 8mL 10mL 0mL 10mL
10mL 0mL 10mL 0mL 10mL
Find β 8mL 2mL
(Hold (Hold (Hold
Constant) Constant) 6mL 4mL Constant)
4mL 6mL
10mL 0mL 2mL 8mL 10mL
When you are changing the concentrations of one of the reactants, it will be necessary to maintain
a constant ionic strength during your dilutions. Use table 1 as a guide for carrying out this process.

1. Prepare a stock solution of 0.05M potassium iodide and another of 0.05M sodium chloride.
This sodium chloride solution will be used to maintain a constant ionic strength when the
amount of potassium iodide is varied.

2. Prepare a stock solution of 0.025M potassium persulfate and another one of 0.075M sodium
chloride. The sodium chloride solution will be used to maintain a constant ionic strength as the
potassium persulfate is varied.

3. Maintain a constant temperature of 298 Kelvin in a constant temperature bath. Mix reactants
while monitoring the reaction (formation of I3-) with the fiber optic spectrometer set up in the
time acquisition mode. Follow the spectrometer operating instructions that are linked to the
lab’s home page (following the link for this experiment). Spectrometer operating instructions
do not need to be included in the procedure for this experiment.

4. Repeat the procedure, using one of the solutions, at two other temperatures that are at least 5
Kelvin apart from each other. Be sure to specify which solution and temperatures you used.

5. When using Beer’s law to convert between absorbance and concentration, use the molar
absorptivity values determined in your “Iodine, Iodide, Triiodide Equilibrium” experiment.

6. Include the following in your report:

a) Reaction orders with respect to I- and S2O8-.

b) The rate law for the reaction.
c) The average rate constant at 298 K (with as much error analysis as possible).
d) Ea (determined from a plot of lnk vs. 1/T). The ambitious are encouraged to perform an
error analysis on this quantity.
e) Any pertinent graphs or diagrams. A plot of the triiodide absorbance spectrum is NOT
needed, however, a plot of absorbance vs. time OR concentration vs. time for one solution
should be included.

ACKNOWLEDGEMENTS

This experiment was made possible by the work of Larry M. Julien, Matt Reuter, and Kelley M.
Smith.

REFERENCES

Levine, Ira N., Physical Chemistry, 5th Ed. McGraw Hill, New York, 2002, 554-555.