Experiment No.

KINETICS: THE OXIDATION OF IODIDE BY HYDROGEN PEROXIDE

A LABORATORY REPORT

Presented to the Faculty of the

Department of Chemistry
College of Science and Mathematics
University of Science and Technology of Southern Philippines

In Partial Fulfillment
of the requirements in
PHYSICAL CHEMISTRY 2 LABORATORY

PHOEBE CUJARDO FONTILLAS

Date Performed: December 07, 2018

Date Submitted: January 11, 2019

 Abstract

Chemical kinetics is the study of chemical reaction rates. Its scope includes understanding how fast a

reaction, along with the factors affecting the rate and determine exactly how a reaction is occurring. The speed

with which the reaction occurs is described by the reaction rate. The factors affecting the reaction rates were the

concentration of reactants, temperature, physical state of the reactants and surface area, and the presence of

catalysts. This experiment studied the kinetics of a reaction between an iodide ion (I-) and a hydrogen peroxide

(H2O2). The average rate constant of the reaction was 2.22. The calculated reaction order with respect to hydrogen

peroxide was 1.50 while the reaction order with respect to the iodide concentration was 1.80. The calculated

activation energy was -41.4 kJ/mol and the pre-exponential factor (A) was 5102518100. Negative activation energy

means that by increasing the temperature, the rate decreases yet it does not conform the Arrhenius equation.

Pre-exponential factor represents the frequency collisions between reactant molecules

 CHAPTER 1

INTRODUCTION

1.1. Rationale of the Experiment

Chemical reaction takes place when a detectable number of molecules of one or more species have lost

their identity and assumed a new form by a change in the kind or number of atoms in the compound and by a

change in structure or configuration of these atoms. Chemical kinetics is the area of chemistry concerned with the

speeds, or rates, at which a chemical reaction occurs. The word “kinetic” refers to the rate of a reaction, or the

reaction rate, which is the change in the concentration of a reactant or a product with time (M/s).

The rates of chemical reactions and the capacity to regulate the rates are critical phases of life. Chemical

kinetics is the study of the rates at which chemical reactions happen, the factors that affect the speed of reactions,

and the mechanisms by which reactions proceed. The reaction rate depends on the reactants, the concentrations

of the reactants, the temperature at which the reaction takes place, and any catalysts or inhibitors that affect the

reaction. If a chemical reaction has a fast rate, a large portion of the molecules react to form products in a given

time period. If a chemical reaction has a slow rate, a small portion of molecules react to form products in a given

time period.

This experiment studied the kinetics of a reaction between an iodide ion (I-) and a hydrogen peroxide

(H2O2). This is a relatively slow reaction. When hydrogen peroxide is added to a solution of potassium iodide, the

iodide ions are slowly oxidized according to the equation:

Molecular equation: 2KI(aq) + 2HCl(aq) + H2O2 (aq) --- I2 (s) + 2H2O (l)

Potassium Iodide Hydrochloric Acid Hydrogen Peroxide Iodine

Net ionic equation: : 2I- (aq) + 2H+ (aq) + H2O2 (aq) --- I2 (s) + 2H2O (l)
Iodide Hydrogen Peroxide Iodine

The rate law for this reaction should include the concentrations of iodide, hydrogen ion, and hydrogen

peroxide. However, if the concentration of H+ is held constant throughout the experiment then its effect
will not appear in the rate law. This results in a relatively simple rate law:

rate = k[I–] n[H2O2]m[H+] p simplifies to:

rate = k'[I–] n[H2O2]m where k' = k[H+] p

In order to study the kinetics of this reaction, or any reaction, there must be an experimental way to

measure the concentration of at least one of the reactants or products as a function of time. In this experiment,

the reactions were done at two different temperatures in order to observe the effect of temperature on the rate

of reaction. In studying the kinetics of a reaction, it is also important to consider the effects that potential catalysts

or inhibitors can have on the reaction rate. These effects were observed by adding one drop of Iron (II) solution

to some of the data runs and comparing the results to data runs with no additives.

1.2 Objectives of the Experiment

The main objective of this study is to determine the rate law for the reaction of hydrogen peroxide. The

experiment addressed the specific objectives:

1. To determine the differential rate law for the reaction between iodide and hydrogen peroxide in an

acidic environment.

2. To determine the activation energy and pre-exponential factor for the reaction.

3. To determine the effect of a catalyst on the rate of reaction.

 CHAPTER 2

METHODOLOGY

2.1 General Information

The following solutions: 1.0M HCl, 1.0M KI, Starch, 0.04M Na2S2O3 and 0.2M H2O2 was prepared by the

students. The members in each groups prepared the following solutions as indicated by Chart 2 (See Appendix

A). After the solutions at the room temperature were prepared, the solution was mixed to create the reaction.

One group member acted as the mixer and one group member acted as the timer. The timer began timing as

the mixer poured the hydrogen peroxide. Then, the mixer gently swirled the contents in the flask that contained

the following solutions. The flask was swirled continuously until the color change was observed. As soon as the

color change was observed, the timer stopped the stopwatch and recorded the time.

2.2 Determining the Rate Law for the Reaction of Hydrogen Peroxide with Iodide

The groups prepared the following solutions as indicated by Chart 2. After the solutions at the room

temperature were prepared, the solution was mixed to create the reaction. One group member acted as the mixer

and one group member acted as the timer. The timer began timing as the mixer poured the hydrogen peroxide.

Then, the mixer gently swirled the contents in the flask that contained the following solutions. The flask was swirled

continuously until the color change was observed. As soon as the color change was observed, the timer stopped

the stopwatch and recorded the time.

2.3 The Effect of Temperature on the Reaction Rate

To study the effect of temperature on reaction rate the experiment was performed at temperatures above

room temperature and at temperatures below room temperature. Since the effect of temperature was to be

measured, the concentrations of all reactants must be constant. To do this, the concentration of experiment #3

from chart 2 (See Appendix A) was chosen.

 The following solutions indicated in Chart 2 experiment #3 (See Appendix A) was prepared by each

group. After the solutions at the room temperature were prepared, the solution was mixed to create the reaction.

The mixture was placed in a cold bath and hot bath. One group member acted as the mixer and one group

member acted as the timer. The timer began timing as the mixer poured the hydrogen peroxide. Then, the mixer

gently swirled the contents in the flask that contained the following solutions. The flask was swirled continuously

until the color change was observed. As soon as the color change was observed, the timer stopped the stopwatch

and recorded the time.

2.4 The Effect of a Catalyst on the Reaction Rate

To study the effect of catalyst on reaction rate the experiment was performed with the addition of Iron

(II) ions in the mixture. Since the effect of catalystwas to be measured, the concentrations of all reactants must be

constant. To do this, the concentration of experiment #3 from chart 2 (See Appendix A) was chosen.

The following solutions indicated in Chart 2 experiment #3 (See Appendix A) was prepared by each

group. After the solutions at the room temperature were prepared, the solution was mixed to create the

reaction. One group member acted as the mixer and one group member acted as the timer. The timer began

timing as the mixer poured the hydrogen peroxide and Iron (II) ions. Then, the mixer gently swirled the contents

in the flask that contained the following solutions. The flask was swirled continuously until the color change was

observed. As soon as the color change was observed, the timer stopped the stopwatch and recorded the time.
 CHAPTER 3

RESULTS AND DISCUSSION

Concentration of Potassium Iodide – 1.0 M

Concentration of Sodium Thiosulfate – 0.04 M

Concentration of Hydrogen Peroxide – 0.02 M

Table 3.1 Effect of Concentration

Experiment # Time of Reaction (s)

1 268.98

2 132.90

3 81.4

4 40.2

5 19.01

The rate law for the reaction between iodide ions and hydrogen peroxide can be determined by carrying

out experiments in which the concentrations of iodide and peroxide are varied. The acidity of the solution must

be maintained at a constant level so that the concentration of H+ is constant. The temperature of the reactants

must be the same for all runs. The rate constant is dependent on the temperature of the solution. Since the heat

of reaction is relatively small for this reaction the temperature should remain relatively constant throughout the

process.

Table 3.2 Initial moles of potassium iodide, sodium thiosulfate and hydrogen peroxide

Expt. # Concentration Volume Moles Concentration of Volume of Moles of Concentration Volume of Moles of
of KI (mol/L) of KI (L) of KI Na2S2O3 (mol/L) Na2S2O3 (L) Na2S2O3 of H2O2 (mol/L) H2O2 (L) H2O2

1 1 0.004 0.004 0.04 0.01 0.0004 0.2 0.01 0.002

2 1 0.008 0.008 0.04 0.01 0.0004 0.2 0.01 0.002

3 1 0.012 0.012 0.04 0.01 0.0004 0.2 0.01 0.002

4 1 0.012 0.012 0.04 0.01 0.0004 0.2 0.02 0.004

5 1 0.012 0.012 0.04 0.01 0.0004 0.2 0.04 0.008

The number of moles of each reactant is found by multiplying the volume of reactant solution added by

the molarity of the reactant.

Table 3.3 Initial Molarity of potassium iodide, sodium thiosulfate and hydrogen peroxide
Expt. # Initial Initial Initial moles Initial Concentration Initial moles Initial Concentration
moles KI Concentration KI Na2S2O3 Na2S2O3 (mol/L) H2O2 H2O2 (mol/L)
(mol/L)

1 0.004 0.02 0.0004 0.002 0.002 0.01

2 0.008 0.04 0.0004 0.002 0.002 0.01

3 0.012 0.06 0.0004 0.002 0.002 0.01

4 0.012 0.06 0.0004 0.002 0.004 0.02

5 0.012 0.06 0.0004 0.002 0.008 0.04

Total volume = 200 mL

To determine the rate law, the initial concentrations of the reactants was determined. This was calculated

by dividing the initial number of moles for each reactant by the total volume of the solution.

Table 3.4 Initial Rate of hydrogen peroxide

Expt. # Moles of H2O2 used Total volume of mixture (L) Molarity of H2O2 (mol/L) Time (s) Rate (M/s)

1 0.0002 0.2 0.001 268.98 3.71775E-06

2 0.0002 0.2 0.001 132.9 7.52445E-06

3 0.0002 0.2 0.001 81.4 1.2285E-05

4 0.0002 0.2 0.001 40.2 2.48756E-05

5 0.0002 0.2 0.001 19.01 5.26039E-05

 The amount of hydrogen peroxide consumed was calculated in order to determine the change in

concentration. The change in concentration of hydrogen peroxide will be needed to calculate the rate of reaction.

The number of moles of peroxide consumed was correlated to the number of moles of thiosulfate. The thiosulfate

ions are the limiting reagent. So once all the thiosulfate ions are consumed, iodine starts to form in the solution.

Iodine is a pale yellow. If starch is added to the solution, then a more dramatic blue solution is formed by the

complex of starch–iodine. The color change is sharp, and the time elapsed to this point is determined simply by

use of a timer. The time from the addition of the peroxide solution to the appearance of the blue color is Δt for

the reaction.

Table 3.5 Logarithms

Expt. # log (rate) Initial Concentration H2O2 log (H2O2) Initial Concentration I- (mol/L) log (I-)
(mol/L)

1 -5.429719989 0.01 -2 0.02 -1.698970004

2 -5.123524981 0.01 -2 0.04 -1.397940009

3 -4.910624405 0.01 -2 0.06 -1.22184875

4 -4.604226053 0.02 -1.698970004 0.06 -1.22184875

5 -4.278982117 0.04 -1.397940009 0.06 -1.22184875

The rate law and reaction order of iodine and hydrogen peroxide was obtained by taking the logarithm.

Log(Rate) = Log (k) + mLog(H2 O2 ) + nLog(I − )

The order of reaction of Hydrogen Peroxide and Iodide was attained by plotting the Log(rate) vs

Log(H2O2)/Log(I) shown in Figure 1 and 2 (See Appendix B).

Base from the equation of the line, the slope (m) in the graph is the order of hydrogen peroxide and

iodide. Base from Figure 1 (See Appendix B), it can be concluded that the reaction order with respect to hydrogen

peroxide is 1.50. By plotting the Log(rate) vs Log(I) shown in Figure 2 (See Appendix B), it can be concluded that

the reaction order with respect to the iodide concentration is 1.80.

 Table 3.6 Rate Constants (k)

Expt. # [H2O2]o [H2O2]m [I]o [I]n Initial Rate k

1 0.01 1.00E-03 0.02 8.75E-04 3.71775E-06 4.25E+00
2 0.01 1.00E-03 0.04 3.05E-03 7.52445E-06 2.47E+00
3 0.01 1.00E-03 0.06 6.32E-03 1.2285E-05 1.94E+00
4 0.02 2.83E-03 0.06 6.32E-03 2.48756E-05 1.39E+00
5 0.04 8.00E-03 0.06 6.32E-03 5.26039E-05 1.04E+00
Value of m = 1.5 Value of n = 1.80
Average
k 2.22E+00

Standard deviation of k 1.125912581

The standard deviation s, is a measure of how close the measured values are to one another. The

standard deviation is a measure of the variability of your measurements. If the only errors made in the experiment

are random errors, then the smaller the standard deviation, the less the random error in your measurements. Base

from the result the standard deviation is very small thus it can be concluded that the rate constant of each

experiments were not different from each other.

Table 3.7 Effect of Temperature

Experiment No. Time of Reaction Temperature

3 150.59 20

50.83 40

The rate of a reaction increases with increasing temperature.

Table 3.8 Rate constant at different temperature

Reaction Temp. Temp. Time (s) Rate (M/s) [I]n [H2O2]m Rate ln k 1/T (k-1)
conditions (⁰C) (K) Constant (K)

Cold 20 293.15 150.59 0.00132811 6.32E- 1.00E-03 2.10E+02 5.34779 0.00341

03
Hot 40 313.15 50.83 0.00393468 6.32E- 1.00E-03 6.23E+02 6.43387 0.00319
03
 Rate constant (k) itself depends on temperature. The relationship between the rate constant and

temperature is reflected in the Arrhenius equation:

𝑘 = 𝐴𝑒 −𝐸𝑎⁄𝑅𝑇

where k is the rate constant, A is called the Arrhenius pre-exponential constant, Ea is the activation energy,

R is the gas constant, and T is the temperature (in units of kelvin). An important point regarding the Arrhenius

equation is that the rate constant (k) depends on temperature and on the value of the activation energy (Ea). The

activation energy can be thought of as a barrier to the formation of products and its value in useful in

understanding the energetics of the reaction. Experimentally, we can determine the value of the activation energy

by measuring the value of the rate constant at several measured temperatures.

Exponential equations like the Arrhenius equation produce curved lines when plotted. It is desirable to

convert the equation into that of a straight line, because then the activation energy and the pre-exponential factor

can be found. The way to convert an exponential equation into a straight line equation is to take the natural

logarithm (ln) of both sides of the equation:

𝐸𝑎 1
ln(𝑘) = − ( ) + ln(𝐴)
𝑅 𝑇

The natural logarithm of k (ln (k)) is plotted versus the reciprocal of the temperature (1/T) a straight line

is produced. The slope, m of the line, is then the negative of the activation energy divided by the ideal gas

constant, and the y-intercept, b, is the natural logarithm of the pre-exponential factor.

From the equation of the line in Figure 3 (See Appendix B), the activation energy and pre-exponential

factor was calculated. The activation energy was -41.4 kJ/mol and the pre-exponential factor (A) was 5102518100.
Table 3.9 Effect of Catalyst

Experiment # Time of Reaction (s)

3 <1

A catalyst is an agent or compound that is added to a process to make a chemical reaction happen more

rapidly. The catalyst can increase the reaction rate of the steam and can participate in the secondary reactions.

The packing can also act as a catalyst to enhance desired chemical transformations. The addition of the iron (II)

solution accelerates the oxidation of iodide by hydrogen peroxide.

 CHAPTER 4

CONCLUSION AND RECOMMENDATIONS

This experiment gave a general knowledge about the different factors that affect the rate of reaction.

Base from the results, the causes affecting the reaction rate were the concentration of reactants, varying

temperature, physical state of the reactants and surface area, and the presence of catalysts. This experiment

studied the kinetics of a reaction between an iodide ion (I -) and a hydrogen peroxide (H2O2). The average rate

constant of the reaction was 2.22. The calculated reaction order with respect to hydrogen peroxide was 1.50 while

the reaction order with respect to the iodide concentration was 1.80. The calculated activation energy was -41.4

kJ/mol and the pre-exponential factor (A) was 5102518100. As the concentration of hydrogen peroxide in the

solution increases the rate of reaction also increases. Rate constant (k) itself depends on temperature. From the

results, the rate of a reaction increases with increasing temperature. Yet, in the experiment there are only two

varying temperatures that was used to determine the rate of reaction. Catalysts work by altering the mechanism

for the reaction, which speeds up the rate of the reaction d lowers the activation barrier. So, reactions with a

catalyst present will have lower activation energy.

References:

 Atkins, Peter, and Julio De Paula. Physical Chemistry for the Life Sciences. Alexandria, VA: Not Avail, 2006.

 Chang, Raymond. Physical Chemistry for the Biosciences. Sausalito, CA: University Science, 2005.

 Laidler, Keith J. Chemical Kinetics.New York : McGraw Hill Book Company, 1950.

 Determination of Reaction Rate and Reaction Rate Constant Practical Report, viewed on 5th December 2018,

<https://dissa4ict.wordpress.com/2013/01/09/determination-of-reaction-rate-and-reaction-rate-constant/>

 Experiment 5, Kinetics: The Oxidation of Iodide by Hydrogen Peroxide, nd, PDF File. Retrieved from
http://www.kbcc.cuny.edu/academicDepartments/PHYSCI/PL/chm12/Documents/
CHM12_Experiment_5_Kinetics.pdf
 APPENDIX A

Chart 2: Volumes of solutions for each experiment (Total volume = 200 mL). Use a 250 mL beaker for the
reaction.
Experiment # Deionized Water (mL) HCl (mL) KI (mL) Starch (mL) Na2S2O3 (mL) H2O2 (mL)
1 170 4 4.0 2 10.0 10.0

2 166 4 8.0 2 10.0 10.0

3 162 4 12.0 2 10.0 10.0

4 152 4 12.0 2 10.0 20.0

5 132 4 12.0 2 10.0 40.0

 APPENDIX B

Experimental Set-up

log(H2O2) vs. log(rate)

0
-2.5 -2 -1.5 -1 -0.5 0
-1

-2

log (rate)
y = 1.5012x - 2.1382 -3
R² = 0.8177 -4

-5

-6
log (H2O2)

(After the addition of Hydrogen peroxide) Figure 1. log (H2O2) vs. log (rate)

log (I-) vs. log(rate) ln(k) vs Temperature

7 y = -4985.1x + 22.353
0
6 R² = 1
-2 -1.5 -1 -0.5 0
-1
5
-2 4
ln(k)
log (rate)

y = 1.8006x - 2.4341 -3 3
R² = 0.7032 2
-4
1
-5 0
0.00315 0.0032 0.00325 0.0033 0.00335 0.0034 0.00345
-6
log (I-) 1/T

Figure 2. log (I-) vs. log (rate) Figure 3. 1/T vs. ln (k)