MULTIMEDIA UNIVERSITY OF KENYA

FACULTY OF SCIENCE & TECHNOLOGY

CHEMISTRY LABORATORY MANUAL

CHEMICAL KINETICS

CHE 2303
 Chemical Kinetics

You may be familiar with acid-base titrations that use phenolphthalein as the endpoint indicator.
You might not have noticed, however, what happens when a solution that contains
phenolphthalein in the presence of excess base is allowed to stand for a few minutes. Although
the solution initially has a pink color, it gradually turns colorless as the phenolphthalein reacts
with the OH- ion in a strongly basic solution.

The table below shows what happens to the concentration of phenolphthalein in a solution that
was initially 0.005 M in phenolphthalein and 0.61 M in OH- ion. As you can see when these data
are plotted in the graph below, the phenolphthalein concentration decreases by a factor of 10
over a period of about four minutes.

Procedure

To 0.005M Solution in phenolphthalein in a beaker add excess of 5mls interval of 0.062M

solution of base.

Experimental Data for the Reaction Between Phenolphthalein and Excess Base

Concentration of
Time (s)
Phenolphthalein (M)
0.0050 0.0
0.0045 10.5
0.0040 22.3
0.0035 35.7
0.0030 51.1
0.0025 69.3
0.0020 91.6
0.0015 120.4
0.0010 160.9
0.00050 230.3
0.00025 299.6
0.00015 350.7
0.00010 391.2

Experiments such as the one that gave us the data in the above table are classified as
measurements of chemical kinetics (from a Greek stem meaning "to move"). One of the goals of
these experiments is to describe the rate of reaction the rate at which the reactants are
transformed into the products of the reaction.
The term rate is often used to describe the change in a quantity that occurs per unit of time. The
rate of inflation, for example, is the change in the average cost of a collection of standard items
per year. The rate at which an object travels through space is the distance traveled per unit of
time, such as miles per hour or kilometers per second. In chemical kinetics, the distance traveled
is the change in the concentration of one of the components of the reaction. The rate of a reaction
is therefore the change in the concentration of one of the reactants (X) that occurs during
a given period of time t.

Problem 1:

Using your data calculate the rate at which phenolphthalein reacts with the OH- ion during each
of the following periods:

(a) During the first time interval, when the phenolphthalein concentration falls from 0.0050 M to
0.0045 M.

(b) During the second interval, when the concentration falls from 0.0045 M to 0.0040 M.

(c) During the third interval, when the concentration falls from 0.0040 M to 0.0035 M.
.

EXPERIMENT 1: RATE OF REACTION OF SODIUM THIOSULFATE AND

HYDROCHLORIC ACID

Rate Laws

AIM
The purpose of this demonstration is to investigate the effect of sodium thiosulfate concentration
on the rate of reaction of sodium thiosulfate with hydrochloric acid. The reaction, which
produces solid sulfur, will be followed by measuring the time
needed for the reaction mixture to become opaque. The results will be analyzed graphically to
determine the order of reaction—the mathematical relationship between the reactant
concentration and the rate.
Concepts
• Kinetics
• Rate law
• Order of reaction
• Concentration
Materials
• Hydrochloric acid solution, HCl, 2 M, 25 mL
• Graduated cylinders, 10-mL, 5
• Sodium thiosulfate solution, Na2S2O3 , 0.15 M, 150 mL
• Overhead projector or light box
• Distilled or deionized water
• Permanent marker
• Beakers, 100-mL, 5
• Stirring rods
• Graduated cylinders, 50- or 100-mL, 2
• Stopwatch or timer

Safety Precautions
Hydrochloric acid solution is corrosive to eyes and skin. It is moderately toxic by ingestion and
inhalation. Sodium thiosulfate solution is a body tissue irritant. The reaction of sodium
thiosulfate and hydrochloric acid generates sulfur dioxide gas, which is a skin and eye irritant.
Perform this demonstration in a well-ventilated lab only. Avoid contact of all chemicals with
eyes and skin. Wear chemical splash goggles, temperature-resistant gloves, and chemical-
resistant apron. Please review current Material Safety Data Sheets for additional safety,
handling, and disposal information.
Procedure
1. Label five 100-mL beakers 1–5 and clean the bottom of each beaker.
2. Draw a large “X” across the bottom on the outside of each beaker. Place the beakers on an
overhead projector stage or a light box so that students can view the “X.”
3. Using separate graduated cylinders for the solution and water, measure and add the required
amounts of 0.15 M sodium thiosulfate and distilled water to each beaker. Be as precise as
possible
Beaker 1 2 3 4 5
0.15 M Na2S2O3 50.0 Ml 40.0 mL 30.0 mL 20.0 mL 10.0mL
Distilled Water 0 mL 10.0 mL 20.0 mL 30.0 mL 40.0mL

4. Have students calculate the final concentration of sodium thiosulfate in each beaker 1–5.
5. Record the following information in a data table: Beaker, volume of Na2S2O3
solution, volume of distilled water, concentration of Na2S2O3 , reaction time (sec), and
1/reaction time (reaction rate). See the Sample Data and Results table in the
Discussion
section.
6. Measure 5.0 mL of 2 M hydrochloric acid into each of five 10-mL graduated cylinders.
7. Starting with beaker #1, carefully add the HCl all in one pour to the sodium thiosulfate
solution. Stir the solution once with a stirring rod and immediately start timing.
8. Stop timing when the black “X” is no longer visible. Record the reaction time in seconds in
the data table.
9. Repeat steps 7 and 8 with beakers 2–5.
10. Calculate 1/reaction time for each trial.

Plot concentration vs. time and concentration vs. 1/time on separate graphs.
EXPERIMENT 2: INVESTIGATING THE EFFECTS OF CONCENTRATION AND
TEMPERATURE ON THE RATE OF A CHEMICAL REACTION

Objective:
To investigate the concentration and temperature effects on the rate of a chemical reaction
Introduction
You have learnt in the classroom session that the rate of a chemical reaction depends on the
concentration of the reactants as well as the reaction temperature. We are going to investigate
this chemical phenomenon. To facilitate our investigation, we need to choose a chemical reaction
that exhibits some easily observable physical changes so that we can monitor the progress of the
reaction conveniently. In this regard we will study the reaction between sodium thiosulphate and
diluted hydrochloric acid.
S2O32-(aq) + 2 H+(aq) SO2(g) + S(s) + H2O(l)
Sodium thiosulphate reacts with diluted acid to give sulphur dioxide, sulphur and water. Both
sodium thiosulphate and diluted hydrochloric acid are colorless solution. Sulphur dioxide is a
very soluble gas and dissolves completely in the aqueous solution. The sulphur formed, however,
is not soluble and will exist in the mixture as white or yellow precipitate (or colloidal). It makes
the reaction mixture becomes opaque as the reaction occurs. Therefore, we can study the reaction
rate by monitoring the opaqueness of the reaction. This can be easily done by measuring the time
taken for forming a certain amount of precipitate.
In the experiment, you will carry out the reaction by mixing the two reactants into a small
beaker, and put the beaker on top of a piece of white paper which has a mark on it. Before the
reaction starts you can see the mark clearly from the top of the beaker through the solution.
However, as the reaction proceeds, sulphur precipitate forms and makes the solution become
more opaque, and so eventually the mark is completely masked. The time taken for the mark to
become totally disappeared indicates how fast the reaction has occurred.
Chemicals:
➢ 0.15 M sodium thiosulphate solution
➢ 1 M hydrochloric acid
Apparatus:
➢ 100 mL beakers
➢ 100 mL measuring cylinder
➢ Thermometer (alcohol, up to 110oC)
➢ Stopwatch
Part A: To study the concentration effect on the rate of a chemical reaction.
In this part of the experiment you will study the concentrate effect on the rate of the above
reaction by varying the concentration of the sodium thiosulphate solution.
Procedure:
1.Take a piece of white paper and make a clear mark on it.
2.Put a dry clean beaker on top of the mark.
3.Measure 60 mL of 0.15 M sodium thiosulphate solution and put it into the beaker.
4.Quickly add 10 mL of 1 M HCl into the beaker in a single portion and start the stopwatch
immediately.
5.Stir the mixture gently with a glass rod for a few seconds.
6.Look at the mark from vertically above the beaker through its content, and record the time
taken for the mark to become totally disappeared.
7.Repeat steps 1-6 by substituting the 60 mL 0.15 M sodium thiosulphate solution with:
Solution Vol. of 0.15M Na2S2O3 Vol. of water Total volume
Solution
A 45 mL 15 mL 60 mL
B 30 mL 30 mL 60 mL
C 15 mL 45 mL 60 mL

Data
1.Time for the disappearance of the cross

Volume of Volume Volume of ) Initial Time for the

Na2S2O3(aq) of water HCl(aq)(mL concentration of disappearance of the
(mL (mL) Na2S2O3(aq) cross/s
(mL)in the First Second Average
reaction mixture trial trial

60 0 10
45 15 10
30 30 10
15 45 10

Data Analysis
1.Calculate the initial concentration of sodium thiosulphate in the reaction mixtures.
Run 1

Run 2

Run 3

Run 4

2.Plot the time required for the disappearance of the cross against the initial concentration of
sodium thiosulphate on a graph paper. Label your graph properly.
3.How is the rate of reaction affected by the concentration of the reactant?

4 .Plot concentration vs. time and concentration vs. 1/time on separate graphs.
EXPERIMENT 3: DETERMINATION OF THE RATE OF OXIDATION OF
IODINE ION BY HYDROGEN PEROXIDE.
Background:

Two important questions may be asked about a chemical reaction:

1. How far or how completely do the reactants interact to yield products?

2. How fast is the reaction?
The first question, how far, is a question of chemical equilibrium which will be studied later on
in the year. The second question, how fast, is the realm of chemical kinetics, the subject of this
experiment.

In this experiment we will see how changing the concentrations of each of the reactants affects
the rate law for the reaction. We will also measure the effect of both temperature and catalytic
activity on the rate.

OBJECTIVE.

In this experiment we will study the rate of oxidation of iodine ion by hydrogen peroxide, which
proceeds according to the equation:

H2O2 + 2I- + 2H+ → I2 + 2H2O

By varying the concentrations of each of the three reactants we will determine the order of the
reaction with respect to each reactant.

To measure the reaction rate we will employ a clever variation of the initial rate method. A
small amount of sodium thiosulfate and starch indicator is added to the reaction mixture.
Thiosulfate ion does not react at an appreciable rate with any of the reactants, but it does react
rapidly with iodine, I2 according the equation:

2S2O32- + I2 → 2I- + S4O62-

As a result, iodine is reduced back to iodide ion as fast as it is formed until all of the thiosulfate
is used up. At this point the solution suddenly turns blue because the iodine concentration
rapidly increases to the point where the iodine forms an intense blue complex with the starch
indicator.

When thiosulfate ion is present in solution, both reactions are happening at the same time. The
reactions can be added together for the following result:

H2O2 + 2I- + 2H+ → I2 + 2H2O

2S2O32- + I2 → 2I- + S4O62-

_______________________________________________
 H2O2 + 2S2O32-+ 2H+ → 2H2O + S4O62-

You should be careful to note that the hydrogen peroxide is not directly reacting with the
thiosulfate, but the result is the same as if it did, and 2 moles of thiosulfate are consumed per
mole of hydrogen peroxide. Therefore the rate the reaction can be written as:

− [H2 O2 ] −1 [S2 O32− ]

rate  =
t 2 t

REQUIREMENTS.

➢ 10-mL graduated pipet

➢ thermometer
➢ timer with a second hand

Chemicals

1. 3% H2O2 stabilized with 0.001-M H2SO4: 1 bottle per 2 groups

2. 0.050-M sodium thiosulfate: 150-mL per group
3. 0.050-M KI: 250-mL per group
4. 0.050-M acetic acid-sodium acetate buffer (0.050-M for both): 500-mL per group
5. 0.1% starch solution (freshly made): 50-mL per group
6. 0.010-M Mo(VI) catalyst (1.76-g/L of ammonium heptamolybate
((NH4)6Mo7O24•4H2O): 10-mL per group
7. 2-M H2SO4

A. Standardization of the Hydrogen Peroxide Solution

1. Fill the buret with 0.050-M Na2S2O3. Then pipet exactly 1.00-mL of the approximately
0.8-M H2O2 solution into a 125-mL Erlenmeyer flask containing 25-mL of H2O.
2. Add 10-mL of 2-M H2SO4, 1-g of solid KI and 3 drops of 3% ammonium molybdate
catalyst.
3. Swirl until the KI dissolves and immediately titrate the brown iodine solution that forms
with 0.050-M sodium thiosulfate until a brown color begins to fade to yellow.
4. At this point add 2-mL of 0.1% starch indicator and titrate till the disappearance of the
blue color. The end point is very sharp and should require a total of 32 to 36-mL of the
0.050-M Na2S2O3. Calculate the exact concentration of the H2O2.

B. Reaction Rate Measurements

Six reaction mixtures will provide the information necessary to determine the effects of the
concentration of H2O2, I-, and H+ on the rate of the reaction.

Make up each reaction mixture in a 250-mL beaker, adding the reactants for each reaction
mixture in the order that they appear in the table (reading from left to right). Read and record the
temperature to the nearest 0.1˚C.

CAUTION: At no time should you allow cross contamination of your glassware. Use one
pipet for the H2O2, one graduated cylinder for the water, etc. Put labels on the glassware so you
do not confuse them.

Reaction Temp H2O 0.05-M 0.3-M 05M .1% .05M .01 0.8-M
Mixture HC2H3O2,
˚C HC2H3O2 KI starch Na2S2O3 Mo H 2O 2
NaC2H3O2
bufffer cat

1 R.T. 75 30 0 25 5 5 0 10

2 R.T. 80 30 0 25 5 5 0 5

3 R.T. 50 30 0 50 5 5 0 10

4 R.T. 30 30 45 25 5 5 0 10

5 R.T. 75 30 0 25 5 5 0 10
+ 10˚

6 R.T. 70 30 0 25 5 5 5 10

To start each reaction add exactly 10 or 5-mL of the H2O2. Start the timer when half of the H2O2
has been added to the mixture. Watch the solution carefully for the sudden appearance of the
blue color and stop the timer when it appears.
C. Interpretation of the Data

1. Calculating the reaction orders and the rate constant

a. Calculate the concentrations of each chemical in the table above. Remember that each
chemical has been diluted by all of the others.
b. Determine the initial rate of each reaction.
− [H2 O2 ] −1 [S2 O32− ]
rate  =
t 2 t

c. Use the method of initial rates to determine the order of the reaction for each reactant.
(This will only apply for mixtures 1-4
d. Once the orders have been determined calculate the value of the rate constant, k. This
should be done 4 times and an average taken.

2. The Effect of Temperature

a. Using reaction mixtures 5 and 1 and determine the ratio of the rates.
rate5 t1 k T5
b. = =
rate1 t5 kT1
c. Determine the rate constant at the elevated temperature

3. Effect of a Catalyst
a. Using the measured reaction times, we can calculate the ratio of the reaction rates from
the data for reaction mixtures 6 and 1
rate6 (catalyzed ) t
b. = 1
rate1 (uncatalyzed) t6

Expectations

1) Formal Lab write-up

2) Data and Calculations
3) Data in neat data tables:
4) Calculations

a) Show how [ ] was determined

b) Show how a, b, c was determined:
c) Show how 2 values of k were determined
d) Determine ratio of rate of R.T. vs R.T. + 10˚
5) Class Data (Including averages and standard deviations)
 a) Value of k (room temperature
b) Value of k (+ 10˚C)

6) Error Discussion
a) In cause-effect data table

7) Questions:
a) Describe why reactions at elevated temperatures happen more rapidly than reactions at
lower temperatures: Use the kinetic molecular theory in your explanation.
b) Describe the effect of a catalyst on a reaction: Include a discussion about what changes
in the rate law.
8) Conclusion
a) Include the final answer: Rate law and2 values of k
b) Comment on the effect of temperature upon reaction rate.
EXPERIMENT 4 : DETERMINATION OF THE RATE CONSTANT

INTRODUCTION

It is not possible for one to predict a reaction rate or rate law from a balanced, overall equation.
Information about the reaction mechanism (pathway) must be known to make such predictions.

Through numerous laboratory studies, experimental rate laws have been found to obey the
general expression: Rate = k {A}x{B}Y{C}Z

where [A], [B], [C], ... represent molarities of all chemical species that affect the rate, and x, y, z,
... are the experimentally determined exponents for each species. (The overall order of the
reaction is equal to the sum of x + y + z +... .) The term k is known as the rate constant for the
reaction.

Usually, when a reaction is initiated, the rate (known as the initial rate) is found to be at its
maximum value. As the reaction progresses, reactants are consumed (lowering their
concentrations) and the rate slows. One can avoid difficult concentration measurements by
monitoring the initial rate. The concentrations at the time of the initial rate are simply the initial
concentrations after taking dilutions into account. If the initial concentration of one reactant is
varied while all others are held constant, then the resulting change in initial reaction rate yields
the order with respect to that one reactant. This is the initial rate method used to determine
reaction order.

In this experiment you will be measuring the initial rate for the iodide ion and persulfate ion,
S2O82-, reaction:

2 I- + S2O82- - I2 + 2 SO42- (1)

To detect the extent to which reaction (1) has proceeded, an additional, simultaneous process
must also occur:

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

OBJECTIVE :

In this experiment we will determine the rate constant at two different temperatures and then
calculate the activation energy of the reaction.

PROCEDURE

1. Work in small groups . Each team needs a timer.

2. Each of the 4 experiments will be performed in duplicate. For each experiment, every team
will need two clean flasks and two clean beakers – these can be wet, but should be well drained.
Potassium chloride and sodium sulfate solutions are used to maintain a constant ionic strength
while diluting reactants in this experiment. Read labels carefully.

4. Obtain reagents and perform one experiment at a time. For experiment 1, prepare 2 flasks,
each containing the volume of potassium iodide, potassium chloride, sodium thiosulfate, and
starch (indicator) solutions provided in the table below.

5. Also for experiment 1, prepare 2 beakers each with the volume of potassium persulfate shown
in the table below.

Volumes of solution, mL

In a flask Room Temperature

EXPERIMENT EXPERIMENT EXPERIMENT EXPERIMENT

1 2 3 4 Ice bath
0.200-M KI 10.0 20.0 20.0 20.0

0.200-M KCl 10.0 0 0 0

0.00500-M 20.0 20,0 20.0 10.0

Na2S2O3

Starch 10drops 10drops 10drops 10.0

In a beaker:

Room temperature

1 2 3 4
Ice bath
0.100-M 20.0 20.0 10.0 20.0
K2S2O8

0.100-M 0 0 10.0 0
Na2SO4

6. Start the timer as the contents of one beaker are added to the contents of one flask. Mix the
reagents by quickly pouring the contents of the flask into the beaker and then returning the
solution to the flask. Allow the flask to sit undisturbed while observing its contents constantly.
Stop the timer when the blue-black color appears. (Constant observation of the flask is necessary
because of the sudden appearance of the blue-black color.) Record the elapsed time in seconds.
Repeat step 6 using the second beaker and flask. Elapsed times for duplicate sets of experimental
conditions should agree within about 2-3 seconds. (If not, do a third trial for that experiment.)

7. Clean your beakers and flasks and allow them to drain well.

8. Repeat steps 4, 5, 6, and 7 for experiment 2 and then experiment 3 with the same mixing
procedure for each experiment.

Note: In experiments 2, 3, and 4, no KCl is required in the flask, but sodium sulfate as well as
potassium persulfate is needed for experiment 3. (Read steps 10 through 12 before doing
experiment 4.)

9. Record the temperature of one of the reaction solutions. (Because all of the solutions have
been sitting at room temperature, you can assume this is the temperature for all the solutions.)

10. For experiment 4, place the volumes of the solutions indicated into clean flasks and beakers.
Fill four of your largest beakers with ice and set the reagent flasks and beakers onto the ice.
Allow the flasks and beakers to remain on ice for at least 5 minutes.

11. Record the temperature of one of the solutions in the ice bath.

12. Repeat step 6. Return the solutions to the ice bath immediately after mixing. When the
reaction flask starts to show a color change, swirl the flask and determine the elapsed time.

13. Perform dilution calculations to determine the molarities at the instant of mixing for the
iodide, persulfate, and thiosulfate ions used in each experiment. You can assume that the 10
drops of starch is 0.5 mL and that the total volume in each experiment is 50.5 mL.

14. Calculate the average elapsed time for each experiment (in seconds).

15. Calculate the Rate for each reaction. Using the rate formular

.-{thiosulfate } initial –{thiosulfate }final / time elapsed

Remember that the final concentration of thiosulfate for each experiment is zero!

16. Using the average rates from experiments 1, 2, and 3 (but not 4), calculate the order of
reaction (1) with respect to the iodide ion and the persulfate ion. Record the orders using the
number of significant figures appropriate for your data.

17. Round off the orders you have determined for iodide and persulfate to the nearest whole
number and then calculate the overall order for the reaction (1). Use the Rate and the rounded
orders to calculate the rate constant, k, for each of experiments 1, 2, and 3. Report your average
value of k (include units).
18. Write the complete rate law for the reaction for the reaction that occurred at room
temperature.

19. Determine the rate constant, k, (include units) for the reaction in the ice bath. Using the
average rate constant from the room temperature experiments and the rate constant from the ice
bath, determine the activation energy of the reaction.

REPORT NAME_______________________

CHEMICAL KINETICS ADM NOS. _____________________

Initial reactant concentrations:

Experiment {iodide } { persulfate } {thiosulfate }

1

Temperature of
solution, (°C)

Temperature of
solution, (°C)

Experiment Time elapsed Time elapsed Average time Rate ,(M/S)

Trial A Trial B ,(s)
1
2
3
4 ice bath

For room temperature data:

Reaction Order

With correct sig figs Rounded to whole numbers

 With respect to Iodide ion

With respect to Persulfate ion

Overall

Value for k from Experiment

1

Value for k from Experiment

2

Value for k from Experiment

3

Average value for k

(including units)

Room Temperature Rate Law

SAMPLE CALCULATIONS (use separate sheets)

Include how you solved for both exponents in this experiment.

REPORT NAME________________________________

CHEMICAL KINETICS (cont’d)

For ice bath data:

Value for k (including units)

SAMPLE CALCULATIONS: (use separate sheets }

Activation Energy, (kJ mol-1)

SAMPLE CALCULATIONS (use separate sheets )

QUESTIONS FOR CHEMICAL KINETICS EXP.

NAME _________________________________

1. The reaction: 2 NO + Cl2 2 NOCl

has been studied and found to be second order with respect to nitrogen monoxide and first order
with respect to chlorine.

a. What is the overall order for the reaction?

b. How does the reaction rate change when the nitrogen monoxide concentration is halved and
the chlorine concentration is doubled? Define terms (e.g., [NO]1 for initial concentration in
experiment 1, [NO]2 for initial concentration in experiment 2, [NO]2 = ½ [NO]1), set up the rate
law ratios and show cancellations for21ExpExp.

2. The initial rate of a reaction is found to increase by a factor of sixteen when the concentration
of one reagent is doubled while all other reagent concentrations are held constant. What is the
order of the reaction with respect to that one reagent? Define terms, set up the rate law ratios and
show cancellations For Exp1 / Exp 2.

3. At 593K a particular decomposition’s rate constant had a value of 2.88×10-4 and at 673K the
same reaction’s rate constant was 1.94×10-3. It was noticed that when the reactant’s initial
concentration was 0.1250 M (with a 593K reaction temperature), the initial reaction rate was
identical to the initial rate when the decomposition was run at 673K with an initial reactant
concentration of 0.04816 M. Recall that rate laws have the form rate = k [A]x and, showing
work, determine the order of the decomposition reaction.

4. The following data was obtained for a reaction in which a chemical, X, decomposed.

Concentration of X (in Molarity) Time (in seconds)

5.00 0

3.52 5.00 * 102

2.48 10.00 * 102

1.75 15.00 * 102

1.23 20.00 * 102

a. Prepare plots of concentration versus time using the provided data in a manner appropriate for
zero, first and second order processes. You must include all three graphs with your report.

b. Based on your graphs, is this reaction zero, first, or second order for X?

c. Determine the slope for the straight line graph. Show how you arrived at the value for the
slope of the line. Calculate the rate constant for this reaction from the slope.

d. Write the complete rate law for the reaction including the value of k (with units).

concentration/pressure or by a temperature change, the system must shift26