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Rate Determination 35
and Activation Energy
An important part of the kinetic analysis of a chemical reaction is to determine the activation
energy, Ea. Activation energy can be defined as the energy necessary to initiate an otherwise
spontaneous chemical reaction so that it will continue to react without the need for additional
energy. An example of activation energy is the combustion of paper. The reaction of cellulose and
oxygen is spontaneous, but you need to initiate the combustion by adding activation energy from a
lit match.
In this experiment you will investigate the reaction of crystal violet with sodium hydroxide. Crystal
violet, in aqueous solution, is often used as an indicator in biochemical testing. The reaction of this
organic molecule with sodium hydroxide can be simplified by abbreviating the chemical formula
for crystal violet as CV.
CV+ (aq) + OH– (aq) → CVOH (aq)
As the reaction proceeds, the violet-colored CV+ reactant will slowly change to a colorless product,
following the typical behavior of an indicator. The color change will be precisely measured by a
Vernier Colorimeter (see Figure 1) set at 565 nm wavelength. You can assume that absorbance is
directly proportional to the concentration of crystal violet according to Beer’s law.

The molar concentration of the sodium hydroxide, NaOH, solution will be much greater than the
concentration of crystal violet. This ensures that the reaction, which is first order with respect to
crystal violet, will be first order overall (with respect to all reactants) throughout the experiment.
You will monitor the reaction at different temperatures, while keeping the initial concentrations of
the reactants the same for each trial. In this way, you will observe and measure the effect of
temperature change on the rate of the reaction. From this information you will be able to calculate
the activation energy, Ea, or the reaction.

OBJECTIVES
In this experiment, you will
React solutions of crystal violet and sodium hydroxide at four different temperatures.
Measure and record the effect of temperature on the reaction rate and rate constant.
Calculate the activation energy, Ea, for the reaction.

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Figure 1

MATERIALS
Vernier computer interface 1 liter beaker
computer ice
Vernier Colorimeter two 10 mL graduated cylinders
Temperature Probe two 100 mL beakers
5 plastic cuvettes 50 mL beaker
0.10 M sodium hydroxide, NaOH, solution watch with a second hand
2.5 × 10–5 M crystal violet solution

PROCEDURE

NOTE: You will be preparing a series of water baths during this experiment.
Measure the temperature of the water baths in whatever way you wish, but make
sure that your measurements are as accurate as possible.
1. Obtain and wear goggles.

2. Connect a Colorimeter to Channel 1 of the Vernier computer interface. Connect a Temperature


Probe to Channel 2. Connect the interface to the computer with the proper cable.

3. Start Logger Pro on your computer. Open the file “35 Activation Energy” from the Advanced
Chemistry with Vernier folder.

4. Set up and calibrate the Colorimeter. Note: You will use this calibration for all four trials in this
experiment. Follow these steps to calibrate the Colorimeter.
a. Prepare a blank by filling an empty cuvette ¾ full with distilled water. Place the blank in the
cuvette slot of the Colorimeter and close the lid.
b. If your Colorimeter has a CAL button, set the wavelength on the Colorimeter to 565 nm, press
the CAL button, and proceed directly to Step 5. If your Colorimeter does not have a CAL button,
continue with this step to calibrate your Colorimeter.
c. Choose Calibrate CH1: Colorimeter (%T) from the Experiment menu and then click
.
d. Turn the wavelength knob on the Colorimeter to the “0% T” position.
e. Type 0 in the edit box.
f. When the displayed voltage reading for Reading 1 stabilizes, click .
g. Turn the knob of the Colorimeter to the Green LED position (565 nm).
h. Type 100 in the edit box.
i. When the voltage reading for Reading 2 stabilizes, click , and then click .

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5. Prepare a cool water bath, ~10°C, in a 1 liter beaker. The bath can be shallow because you will
be using it to cool the two 10.0 mL aliquots of reactants. Immerse the tip of a Temperature
Probe in the cool water bath.

6. Ready the NaOH and crystal violet solutions for the first trial.
a. Use a 10 mL graduated cylinder to obtain 10.0 mL of 0.10 M NaOH solution. Transfer the
solution to a 100 mL beaker. CAUTION: Sodium hydroxide solution is caustic. Avoid
spilling it on your skin or clothing.
b. Use another 10 mL graduated cylinder to obtain 10.0 mL of 2.5 × 10–5 M crystal violet
solution. Transfer the solution to a second 100 mL beaker. CAUTION: Crystal violet is a
biological stain. Avoid spilling it on your skin or clothing.
c. Place the two 100 mL beakers of reactants in the water bath. Make sure that the level of the
solutions on the beakers is below the level of the water bath. The beakers should be in this
water bath for at least one minute.
7. Conduct the first trial. Be ready to time the reaction.
a. Check the temperature of the water bath; it should be holding steady at or near 10°C.
j. When you are certain that the reactants have been cooled to ~10°C, pour the NaOH and crystal
violet solutions into the 50 mL beaker. Start timing the reaction using the second hand on your
watch. You will allow the reaction to run for one minute before proceeding to Part c of this step.
Stir the reaction mixture with the Temperature Probe.
k. After one minute, record the temperature of the mixture.
l. Fill a clean, dry cuvette about ¾ full with the reaction mixture. Place the cuvette in the
Colorimeter. Close the lid on the Colorimeter.
m. Click to begin collecting absorbance data.
n. Collect data for 60 seconds. Observe the progress of the reaction in the beaker.
o. When data collection is complete, carefully remove the cuvette from the Colorimeter. Dispose
of the contents of the beaker and cuvette as directed.
8. Because the reaction is first order with respect to crystal violet, you can determine the rate
constant, k, by plotting a graph of ln Absorbance vs. time.
a. Choose New Calculated Column from the Data menu.
p. Enter “ln Absorbance” as the Name, and leave the unit blank.
q. Enter the correct formula for the column into the Equation edit box by choosing “ln” from the
Function list, and selecting “Absorbance” from the Variables list. Click .
r. Click on the y-axis label. Choose ln Absorbance. A graph of ln absorbance vs. time should now
be displayed.
s. Click the Linear Regression button, . From the slope value, determine the rate constant, k, and
record it in your data table.
t. Close the Linear Regression box by clicking the X in the corner of the box.
9. To prepare to collect data for another trial, choose Store Latest Run from the Experiment menu.
For the next trials that you do, you will monitor the progress of the reaction on the graph of ln
absorbance vs. time.

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10. You are now ready to perform another trial. The next trials will be at ~15°C, ~20°C, and ~25°C.
a. Prepare the next water bath, ~15°C, by adding warm water to the 1 liter beaker.
u. Add 10 mL of NaOH and 10 mL of crystal violet solutions to their respective 100 mL beakers,
and lower them into the water bath as you did before.
v. When you are certain the reactants have cooled to the temperature of the water bath, pour the
contents of both beakers into the 50 mL beaker.
w. Stir the contents of the 50 mL beaker with your Temperature Probe. After one minute, record
the temperature of the mixture.
x. Fill a clean, dry cuvette about ¾ full with the reaction mixture. Place the cuvette in the
Colorimeter. Close the lid on the Colorimeter.
y. Click to begin collecting ln absorbance data.
z. When the data collection is complete, carefully remove the cuvette from the Colorimeter.
Dispose of the contents of the beaker and cuvette as directed.
aa. On the plot of ln absorbance vs. time for your latest trial, click the Linear Regression button, .
Record the rate constant, k, in your data table.
bb. Close the Linear Regression box by clicking the X in the corner of the box.
11. Repeat Steps 9–10, using a water bath at ~20°C.

12. Repeat Steps 9–10, using a water bath at ~25°C.

13. Print a graph of ln absorbance vs. time, with all four trials displayed on the graph. Identify each
plot with its temperature value, by choosing Text Annotation from the Insert menu.

DATA TABLE
Trial Temperature Rate constant, k
(°C) (s-1)

DATA ANALYSIS
1. Plot a graph of your data above, using Temperature (°C) as the x-axis, and the rate constant, k,
as the y-axis.

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a. Disconnect your Colorimeter and Temperature Probe from the interface.


b. Choose New from the File menu. An empty graph and table will be created in Logger Pro.
c. Double-click on the x-axis heading in the table, enter a name and unit, then enter the four
values for Temperature (°C) from your data table above.
d. Double-click on the y-axis heading in the table, enter a name and unit, then enter the four
values for the rate constant from your data table above.

2. In order to determine the activation energy, Ea, you will first need to plot the natural log of k vs.
the reciprocal of absolute temperature.
a. Choose New Calculated Column from the Data menu.
b. Create a column, ln rate constant, k.
c. Create a second column, reciprocal of absolute temperature, 1/(Temperature (°C) + 273).
d. On the displayed graph, plot ln rate constant on the y-axis and reciprocal of absolution
temperature on the x-axis by clicking on the respective axes labels. Autoscale the graph if
necessary.

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3. Calculate the activation energy, Ea, for the reaction. To do this, first perform a linear fit on the
graph you created in Step 2 above. Use the slope, m, of the linear fit to calculate the activation
energy, Ea, in units of kJ/mol. Note: On a plot of ln k vs. 1/absolute temperature, Ea = m × R.

4. A well-known approximation in chemistry states that the rate of a reaction often doubles for
every 10°C increase in temperature. Use your data to test this rule. Calculate the ratio of the rate
constant at ~20°C to the rate constant at ~10°C. Then calculate the ratio of the rate constant at
~25°C to the rate constant at ~15°C. How close were these values to a ratio of 2? (Note: It is not
necessarily equal to 2.00; this is just an approximate value, and depends on the activation energy
for the reaction.)

5. Using the rate constant and precise temperature value for the trial that was done at room
temperature (~20°C), as well as the Ea value you obtained in Step 3 above, calculate what the
rate constant would be at 40°C.

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