Module 04: Chemical Kinetics: Determination of Reaction Order

Prelab Study Guide I (Introduction, Materials and Methods)

OUTLINE LEARNING OBJECTIVES

Introduction At the end of this exercise, the student should be
Materials and Methods able to:
Reagents ● write the rate law of the reaction;
Glassware and Apparatus ● calculate the concentrations of reactants
Procedure in reaction mixtures using dilution
Determination of Reaction Order equation;
Waste Management ● use the method of initial rates to determine
Supplementary Resource the order of the reaction; and
Experimental Data ● interpret the rate law obtained.
Data Treatment
Postlab Questions

I. INTRODUCTION

The reaction mechanism of a certain chemical reaction shows the conversion of reactants to products. A reaction mechanism can b

Figure 4-1. Reaction pathway for a typical reaction.

Chemical kinetics is a branch of chemistry which deals with elucidation of these reaction mechanisms. Among others,
chemical kinetics helps in the deduction of the fate of the reactants. Several variables can be altered to see how the
reactants can overcome the Ea for the reaction to proceed. These variables include, but not limited to, temperature,
concentration, and the presence of a catalyst. Effective collisions, collisions that are observed when the reactants have
enough energy and proper orientation (Figure 4-2), are needed by the reactants to gain enough energy in overcoming
the Ea.

Temperature works through increasing the kinetic energy of the reactants and resulting to more collisions. Adding more
reactants in a given volume of the reaction mixture could provide more collisions in the limited space they are in. A
catalyst, however, does not work by increasing effective collisions but through looking for an alternative path with lower
Ea.
 Figure 4-2. Illustration of effective and ineffective collisions.

Manipulating the concentrations of the reactants can be considered as one of the most convenient means to understand
reaction mechanisms and to further enhance the speed of the reaction. To start with, the reaction can be summarized
into a rate law. A rate law is written as the rate of reaction being equal to the concentration of the reactants at constant
temperature. Rate constant acts as a proportionality constant as seen in the equation below:

Rate = k[A]a[B]b (Eqn 4-1)

The exponents a and b are the orders of the reaction with respect to reactants A and B, respectively. The order of the
reaction dictates how the concentration of a reactant affects the speed of conversion of reactants to products.

In this exercise, the order of the reaction of acetone with iodine (Rxn 4-1) in an acidic medium will be determined.

(Rxn 4-1)

Each reactant has its own order and can be obtained by several methods, one of which is the Method of Initial Rates.
In this process, the initial concentrations of the reactants are kept constant to determine the reaction rate. After that, a
series of similar experiments is conducted with one of the reactants’ concentration being manipulated. An example is
shown below to illustrate the calculations needed to come up with the rate law using the Method of Initial Rates.

EXAMPLE. !"# %&' ()*'+ #',-%)"+. / 0 12

The following data were obtained for the formation of C.

Run Rate Initial Concentration of A Initial Concentration of B
(mole L-1sec-1) (mole L-1) (mole L-1)
1 2.73 0.100 0.100
2 6.14 0.150 0.100
3 2.71 0.100 0.200

Write the rate law for the reaction. Determine the order of the reaction.

SOLUTION. The rate law is given in equation 4-1. To obtain the value of a (the order of reaction with respect to A), take
the ratio of the rate laws for the two runs where the concentration of B is the same. Using run 1 and run 2, the ratio can
be written as:

𝑟1 𝑘[𝐴] 𝑎[𝐵] 𝑏
1
=
𝑟2

Then, the numerical values are substituted into the equation.

 2.73 𝑚𝑜𝑙𝑒 𝐿%& 𝑠𝑒𝑐 %& 𝑘(0.100 𝑚𝑜𝑙𝑒 𝐿%& )' (0.100 𝑚𝑜𝑙𝑒 𝐿%& )(
=
6.14 𝑚𝑜𝑙𝑒 𝐿%& 𝑠𝑒𝑐 %& 𝑘(0.150 𝑚𝑜𝑙 𝑒 𝐿%& )' (0.100 𝑚𝑜𝑙𝑒 𝐿%& )(
The equation can be simplified to
2.73 0.100'
6.14 = 0.150'
2.73 0.100
'

=
6.14
The value of a is obtained by taking the natural logarithm of both sides of the equation:

2.73
0.100
𝑙𝑛 ; < = 𝑎 𝑙𝑛 ; <
6.14
0.150
2.73
𝑙𝑛 ? 6.14@

In this case the reaction is second order with respect to A. A similar strategy can be employed to determine the value of b
using the data from runs 1 and 3 where the concentration of A is just the same and B varies. Employing this method to
obtain b results in a value of zero. This implies that the reaction is zero order with respect to B or the rate is independent
of the concentration of B.
The rate constant can now be determined by substituting the values of a and b in any of the runs. Using the data from
run 1:
2.73 mole L-1sec-1 = k (0.100 mole L-1)2 (0.100 mole L-1)0
k= 273 mole L-1sec-1

The data generally suffers from experimental error. Hence, it is best to calculate the rate constant for each run and use
the average value. The average value for k is 272 L mole -1sec-1. Hence the rate law for the reaction is

Rate = 272 L mole-1sec-1[A]2[B]0 or Rate = 272 L mole-1sec-1[A]2

II. MATERIALS AND METHODS

●
4M acetone ● 1 M HCl ● 0.0012 M I2 ● starch
A. REAGENTS
B. GLASSWARE AND● APPARATUS
●
test tube ● test tube rack 10-mL graduated ●
125-mL Erlenmeyer
cylinder flask

C. PROCEDURE

1. Determination of reaction order

Prepare five (5) Erlenmeyer flasks and five (5) test tubes and number them from 1 to 5. Place the designated amounts of
HCl, I2, starch solution and water to each flask and the corresponding amounts of acetone into a test tube (see Table 4-
1). Cover the flask and test tube using a tissue then place the flasks and test tubes containing acetone in a water bath for
five
(5) minutes. Transfer the acetone into their corresponding flask. Cover the flask and swirl the mixture until the dark blue
color disappears (a white background is helpful). Record the time it took for the dark blue color to disappear. Start taking
note of the time as soon as the acetone has been transferred into the Erlenmeyer flask.
 Table 4-1. Amount of acetone, HCl, I2, starch solution and water for each run.
Volume, mL
4.00 M 0.00120 M I2 1.00 M HCl Starch dH2O
Run
acetone solution

1 2.00 2.00 2.00 2.00 17.00

2 4.00 2.00 2.00 2.00 15.00
3 2.00 2.00 4.00 2.00 15.00
4 2.00 4.00 2.00 2.00 15.00
5 3.00 3.00 3.00 1.00 15.00

2. Waste Management

Dispose the collected product into E501 or “Iodine-Containing Wastes”.

3. Supplementary Resource

You may watch this video (https://youtu.be/KkpeiuelvTI) to see how the experiment is done on the lab. In this video,
starch solution was not added to the mixture.

III. Experimental Data

Table 4-2. Time elapsed for each run

Run Time elapsed

(sec)
1 258
2 130
3 133
4 515
5 189

IV. DATA TREATMENT

Determine the concentration of each component (C 2) in the final mixture for each run (refer to Table 4-1 for the total
volume (V2) of the mixture, and the initial concentration (C 1) and volume (V1) of each component).

C1V1 = C2V2
Example:
1. For the concentration of acetone in the final mixture for Run 1,
C1V1 = C2V2
[acetone]=

2. Calculate for the reaction rate per run using the concentration of iodine and time elapsed.
3. Determine the reaction order with respect to I 2. Also determine the reaction order with respect to C 3H6O and the
reaction order with respect to HCl. Round off your answers to the nearest whole number. Refer to the sample
calculation in the Prelab SG I as your guide.
 4. Calculate for the rate constant for each run using the reaction orders obtained ( use rounded off values of
reaction orders).
5. Take the average of the rate constants.
6. Determine the rate law of the reaction.

V. POSTLAB QUESTIONS
1. Why were the reagents equilibrated in water bath before mixing?
2. What is the purpose of starch in the experiment?
3. What will happen to the reaction time and reaction rate if the concentration of one of the reactants is doubled
while keeping everything the same?
4. Cite possible sources of error in the experiment.

VI. REFERENCES

 BROWN TL, LEMAY HE, BURSTEN BE, MURPHY CJ, WOODWARD, PM. 2012. Chemistry: The Central Science. 12 th ed.
Glenview, Illinois: Pearson Prentice Hall. p. 530.
 DAVIS RE, FREY R, SARQUIS M, SARQUIS JL. 2006. Modern Chemistry. Austin, Texas: Holt, Rineheart and
Winston. p. 345-346.
 NEGI AS, ANAND SC. 1985. A textbook of Physical Chemistry. 1985. 1 st ed. Delhi, India: New Age International
(P) Ltd., Publishers. p. 440-441.