Engineering Chemistry DPT

Physical Chemistry Practical

Second Stage

Experiment 4:
Determination the activation energy

By
MSc-Suzan Sidqe Saleem
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Objectives

1. Determine the activation energy for the Halogenation of Acetone

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 Introduction

Activation energy is defined as the minimum energy barrier that must be overcome for a chemical
reaction to take place. It is usually denoted as Ea, and given in unit of kiloJoule, kJ/mol. For a
chemical reaction, an appreciable number of molecules with the energy equal to or greater than
activation energy should be exist in the system.

In order for a reaction to occur, the reactant particles must collide according to the collision theory.
However, not all collision are able cause the reaction to happen, only a certain collisions in the
system can cause chemical reaction, which is called effective collision. The effective collisions of
molecules must collide with the correct orientation and sufficient energy to overcome the activation
energy barrier. The energy is needed to break the existing bonds and form the new bonds of the
molecules which resulting in the formation of products

The activation energy of a reaction can be measured by using Arrhenius equation as

shown in the equation below:

k = Ae-Ea/RT
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where k = rate constant
T = absolute temperature
Ea = energy of activation
R = gas constant

The pre-exponential term, A is the number of collisions per sec times.. However, according to the
equation, the dependence of k on temperature is dominated by the strong exponential term, so the
dependence of A on temperature is usually ignored as a first approximation. By taking logarithms of
both sides

k = Ae-Ea/RT

Log10 k = -Ea / 2.303RT + log 10 A

= -Ea /2.303RT + constan
So, when a reaction has a rate constant that obeys Arrhenius equation, a plot of log 10 k versus 1/T
gives a straight line. The gradient of the straight line is –Ea / 2.303R while the interception of the
straight line on the y-axis of the graph can be used to determine the values of log 10 A
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 Now, the rate of reaction is higher when the time taken for a fixed amount of reaction to
complete is shorter. This makes the time taken, t to complete a fixed amount of reaction is
inversely proportional to the rate constant, k.

T α 1/k
or t = constant/k
By taking logarithms of both sides,
Log10 t = - log10 k + constant
= Ea / 2.303RT + constant

A plot of log10 t versus 1/T gives a straight line as well and the slope of the graph is Ea / 2.303R.
Thus, if t is measured at several temperatures then the energy of activation can be found

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 Experimental Procedure:

Acetone is halogenation by iodine in acidic media, The acid acts as a catalyst for the reaction

CH3COCH3 + I2 →CH2ICOCH3 + HI

1-Obtain 100 mL of 4.0 M acetone, 100 mL of 1.0 M HCl and 50 mL of I2 solution

in beakers. Keep a watch glass over the reagent beakers while not in use.
2-Keeping a reaction at a fixed temperature takes some experimental care. It is no good to
have a flask in a water bath at 50 C and then place reagents that are at 22 C in the flask
and expect to know the temperature.

3-In a 1000 mL beaker prepare a water bath at room temperature.

4-Clamp your 125 mL Erlenmeyer flask into the water bath along with a thermometer and a test tube to
hold your I2 solution.
5-Measure and pour the amounts of acetone and HCl that you will use in the reaction into the 125 mL
reaction flask. Pour into a clean test tube the amount of I2 to be used in the reaction. Clamp each solution into
the water bath and let it sit for five minutes to equilibrate to the bath temperature.
6-After the 5 minutes of equilibration, record the water bath temperature. This will be the reaction
temperature. Remove the I2 solution from the clamp and quickly add it to the reaction mixture. At the
same time you add the I2 solution, begin timing the reaction. Swirl the reaction mixture initially by
swirling the whole ring stand. After an initial shake the reaction can be left to sit. When the iodine color
is gone the reaction is complete.
When the reaction is completed, clean your glassware and prepare to run the reaction in a new water bath. The
I2 test tube does not need to be cleaned since it will always contain the same concentration of liquid.

From the reaction time and the initial I2 concentration, determine the reaction rateat this
temperature.

7-Steps (1) to (6) was repeated, maintaining the reaction temperature at about 10C.

After determining the reaction rate at four different temperatures between 10, 50C, clean your glassware
and return your 1000 mL beaker, thermometer and ringstand to the front of the room.
Calculation

Temp.(k) 1\T Time 1\t Log 1\t

40
10

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