Exp 13 Kinetics of Crystal Violet Instructions

Experiment
13:
Kinetics of the Reaction of Crystal Violet and Sodium Hydroxide
OBJECTIVES
 Illustrate the principles of chemical kinetics using the reaction of crystal violet and
sodium hydroxide
 Determine the rate constant and order with respect to the crystal violet and hydroxide
 Determine the effect of temperature on the rate of reaction and calculate the activation
energy.
VIDEO: Colorimeter and Cuvette Technique
THEORY
Reading : Textbook (Gilbert, T.R. Chemistry: An Atoms‐Focused Approach, 1st ed.)
 Section 13.2 Reaction Rates
 Section 13.3 Effect of Concentration on Reaction Rate
 Section 13.4 Reaction Rates, Temperature and the Arrhenius Equation
 Section 13.5 Reaction Mechanisms
 Section 13.5 Catalysts
Kinetics of the reaction of crystal violet, [C(C6H4N(CH3)2)3]+, and hydroxide ion will be studied.

Figure 13‐1: Structure of Crystal Violet Cation
[C(C6H4N(CH3)2)3]+(aq) + OH‐(aq) → [C(C6H4N(CH3)2)3]OH(aq) (13‐1)
Equation 13‐1 may be simplified by writing CV instead of the crystal violet formula as follows.
CV+(aq) + OH‐(aq) → CVOH(aq) (13‐2)
purple colorless colorless

Determination of Order of Reaction
The rate of the reaction with respect to the colored cation CV+ is given below. Note that the
negative sign is required because the crystal violet cation is a reactant which is consumed.
Exp 13 Page 1 Dec. 5, 2017 by Sheppard
[CV  ]
Rate   (13‐3)
t
The rate law for the reaction is: Rate = k [CV+]X [OH–]Y (13‐4)
k is the temperature‐dependent rate constant, X is the reaction order with respect to CV+, and Y
is the reaction order with respect to hydroxide ion, OH–.
The “isolation method” will be used to find the values of k, X and Y under experimental
conditions such that one reactant (OH–) is present in large excess. [OH–]o >> [CV+]o. The “o”
subscripts indicate initial values (values at time t = 0). Under these conditions the concentration
of hydroxide ion will change only minimally as the reaction proceeds and may be assumed to
remain constant, in which case the rate law may be reformulated as follows.
Rate = k [CV+]X [OH–]Y = kps[CV+]X (13‐5)
In equation 13‐5, kps is the pseudo‐rate constant when [OH–]o >> [CV+]o.
kps = k[OH–]Y  k [OH–]oY (13‐6)
Combining equations 13‐3 and 13‐5 yields the following equation for rate.
[CV  ]
Rate   = kps[CV+]X (13‐7)
t
Integration of this rate law yields the following integrated rate laws for each likely order of
reaction. Note that third order is possible but extremely unlikely.
Table 13‐1: Dependence of Rate Law on Order
Order of Reaction with Integrated Rate Law Linear Graphs to Confirm Slope of
Respect to CV+ (X) the Associated Order Linear Graph
0 [CV+]t = –kpst + [CV+] +
[CV ]t versus t –kps
1 ln[CV+]t = –kpst + ln[CV+] ln[CV+]t versus t –kps
2 1/[CV+]t = kpst + 1/[CV+] 1/[CV+]t versus t kps

Each of the three graphs will be constructed and the degree of linearity will be assessed. Each
linear fit gives a correlation coefficient and RMSE value. The correlation coefficient would
provide a consistent measure of the “goodness of fit” but is not sensitive enough to detect
small differences. The root mean square error (RMSE) is a preferable criterion but its
significance varies with the magnitude of the measured variable. (For instance, a RMSE error of
say 0.1 is more significant if the mean value of the data set is 10 than if it is 1000). To deal with
this, the RMSE value will be divided by the value of the absorbance at the mid‐point (7 minutes)
of each test. The lower the error obtained by this method the better the linear fit.
The order with respect to hydroxide (Y) is determined by first taking the natural log of equation
13‐6.
ln kps = ln (k [OH–]oY) (13‐8)
Invoking the mathematical rules of logarithmic functions gives the following 3 equations.
ln kps = ln k + ln [OH–]oY (13‐9)
ln kps = ln k + Y ln [OH–]o (13‐10)
ln kps = Y ln [OH–]o + ln k (13‐11)
According to equation 13‐11, a graph of ln kps versus ln [OH‐] will yield a straight line with slope
of Y. The order with respect to [OH‐] is the integer closest to the value of the slope. Also, the
rate constant, k, may be obtained by mathematical manipulation of the y‐intercept of the same
graph.
Determination of Activation Energy
Every reaction has a minimum energy which must be overcome for the reactants to become
products. This energy bump or activation energy, Ea, is a constant for a particular reaction even
when temperature is changed. However, as temperature is increased, molecules have more
kinetic energy and a greater fraction of them have energy greater than the activation energy
leading to a faster reaction rate. The rate constant, k, increases as shown in the following
Arrhenius equation.
k  Ae  E a / RT (13‐12)
To obtain a form of the equation which is more easily graphed take the natural log of both sides
and rearrange to form the following equation.
Ea  1 
ln k      ln A (13‐13)
R T 
A graph of ln k versus 1/T (in Kelvin) allows calculation of the activation energy of the reaction.
Note that R = 8.3145 J mol‐1 K‐1.
According to Table 13‐1, a graph of ln[CV+]t versus t will give a slope of –kps. The rate constant,
k, (rather than pseudo rate constant) can be found from equation 13‐6. Repeating these steps
at each temperature will give a series of k values at varying temperatures which can be graphed
according to equation 13‐13 to find the activation energy.
Monitoring the Reaction by Colorimetry

Due to the colored nature of the crystal violet ion, the reaction may be followed by measuring
absorbance. The visible spectrum for crystal violet in aqueous solution is shown in Figure 13‐2
(next page). The Lab Pro colorimeters offer wavelength choices of 430, 470, 565 and 635 nm, of
which the 565 nm wavelength is the most suitable.
The test concentrations used are low enough that Beer’s Law is obeyed. Beer’s Law states that
absorbance, A, increases linearly with concentration, c, as shown in equation 13‐12.
A = ε b c (13‐14)
where ε is the molar absorptivity (units are L mol‐1 cm‐1) and b is the path length or distance
light must travel (in cm) through the solution. Since the absorbing species and pathlength are
constant, the following may be written.
A = (constant) [CV+] (13‐15)
Thus, in the determination of the order X, the absorbance, A, may be substituted for [CV+] since
the two are directly proportional. In cases where the Beer’s Law constant was needed, it may
be calculated by substituting the absorbance and concentration of crystal violet (at time zero)
into equation 13‐13.

Figure 13‐2: The Visible Spectrum of Crystal Violet
EXPERIMENT 13A PROCEDURE DAY 1

Setup of Logger Pro
1. In your personal computer drive, create a new folder entitled “Crystal Violet Lab”.
2. Connect the colorimeter to Lab Pro Channel 1 (or Go! Link). Open the Logger Pro program
which should auto‐detect the presence of the colorimeter.
3. On the colorimeter, set the wavelength to 565 nm.
4. If the digital readout box does not display Absorbance then double click on the box, select
Column… Absorbance and click OK.
5. Fill a cuvette with deionized water and place it in the colorimeter. Press the “CAL” button
until the red indicator light on the colorimeter begins to flash and then release the button.
An absorbance value of close to 0.000 should now appear in the Logger Pro program.
NOTE: the same cuvette should be used for all runs, so set this cuvette upside to dry in
anticipation for its use later.
6. Click Experiment… Data Collection. De‐select the Sample at Time Zero option and set a
Duration of 15 minutes and a Sampling Rate of 1 sample/minute.
7. Double click in the Graph field to open the Graph Options window. Under the Graph
Options tab, deselect Mouse Position and Delta, deselect Connect Points and select Point
Symbols. You will set a title later. Click Done.
8. Save four copies of this file as “Solution1”, “Solution2”, “Solution3”and “Solution1temp” in
the Crystal Violet Lab Folder.
Solution Preparation
1. In a clean, dry 250 mL beaker, obtain about 100 mL of the prepared stock solution of
2.00 × 10‐5 M crystal violet, [C(C6H4N(CH3)2)3]Cl.
2. In a clean, dry 250 mL beaker, obtain about 80 mL of the prepared stock solution of
0.0200 M sodium hydroxide, NaOH.
3. Obtain and label the following volumetric pipets: 20.00 mL (label CV), 10.00 mL (label
NaOH) and 5.00 mL (label NaOH). Rinse each pipet with the appropriate solution three
times.
4. Open the file entitled “Solution1”.
5. Using a volumetric pipet, add the volumes of solutions indicated in Table 13‐2 into two
separate dry beakers.
Table 13‐2: Preparation of Solutions
Add to a 50 mL Beaker Add to a 100 or 150 mL Beaker
Solution Volume of 2.00 × 10 M ‐5
Volume of 0.0200 M
Volume of Water (mL)
Crystal Violet (mL) NaOH (mL)
1 20.00 0.00 20.00
2 20.00 10.00 10.00
3 20.00 15.00 5.00
6. Place the beaker containing the pipetted NaOH and water on the magnetic stirrer, add a stir
bar and turn on the stirrer.
Effect of Concentration on Reaction Rate

Remember to record observations for all runs.
7. The next few steps require a plan of your time and roles before you begin. Rapidly add the
contents of the 50 mL beaker to the stirred beaker and simultaneously click Collect. After 20
seconds of stirring, rapidly transfer a portion of this solution to a cuvette and place the
cuvette in the colorimeter (within 1 minute from the start if possible). Rinse and dry the
beakers between runs.
 Time saving tip: While LoggerPro is collecting data, pipet the next set of solutions.
8. When data collection has stopped at the end of the 15 minute test period, click File... Save.
For solution 1 only, print the graph in the appropriate format.
9. Open the “Solution2” file. Thoroughly rinse the cuvette and re‐check the calibration of the
colorimeter against the blank water sample.
10. Repeat the experiment as described in steps 5 to 8 except Solution 2 will be prepared.
11. Open the “Solution3” file. Thoroughly rinse the cuvette and re‐check the calibration of the
colorimeter against the blank water sample.
12. Repeat the experiment as described in steps 5 to 8 except Solution 3 will be prepared.
13. Place a thermometer in one of your solutions and record the temperature.
Effect of Temperature on Reaction Rate

14. Open the “Solution1temp” file. Thoroughly rinse the cuvette and re‐check the calibration of
the colorimeter against the blank water sample.
15. Repeat steps 5 and 6 to prepare a fresh Solution 1 again.
16. ODD‐numbered bench: You will heat both beakers on a hotplate to a temperature above
room temperature (ask your Lab Instructor for your temperature). Record the temperature
just before mixing.
EVEN‐numbered bench: You will cool both solutions to a temperature below room
temperature (ask your Lab Instructor for your temperature) by placing the beakers in a cool
water or ice‐water bath depending on how low the temperature you are assigned. Record
the temperature just before mixing.
17. For this alternate temperature experiment, the temperature will change rapidly when the
solution is removed from the water bath. A shorter run time will decrease error.
Click Experiment… Data Collection. Set a Duration of 200 seconds and a Sampling Rate of 1
sample/second.
18. Rapidly add the contents of the 50 mL beaker to the stirred beaker and simultaneously click
Collect. Immediately and rapidly transfer a portion of this solution to a cuvette and place
the cuvette in the colorimeter (within 30 seconds from the start if possible). Rinse and dry
the beakers between runs.
19. When data collection after 200 seconds, click File... Save.
20. Record the temperature in the cuvette immediately after 200 seconds has elapsed.
21. Print this graph in the appropriate format.
22. Ensure your data AND both graphs are signed by the TA or Instructor before you leave.
SHARING FILES
The person who logged into the computer will have their files on their personal SMU drive.
However, to prevent loss of files, each student should email the files to themselves. This
ensures each student has files to work with if a partner is absent the following week and
regardless of who logs into the computer.
CLEAN UP
 Disconnect the colorimeter from the Lab Pro interface.
 Dispose of all waste in the provided waste container.
 Complete the list of items in the Post Lab Checklist taped to your benchtop.
 Log off your work station.
Experiment 13B:
Kinetics of the Reaction of Crystal Violet and Sodium Hydroxide
PROCEDURE DAY 2: DATA ANALYSIS

Note: There are many graphs to create. Ensure each graph is represented appropriately with
the data spanning the entire graph sheet and any extraneous information removed.
Note: All students in a group must be actively involved in analyzing the data. You are
responsible for learning how and why these graphs are created. Refer to the theory section as
you create the graphs to determine the meaning of the slopes and intercepts. Logger Pro
graphing and manipulation (possibly this lab) is part of the lab skills exam.
Proceed through the following instructions to answer the questions in Part 2. Data Analysis.
You will likely have time to complete the entire report.
EFFECT OF CONCENTRATION ON REACTION RATE

Determination of the Value of X (order of CV + )
1. Open the “Solution1” file. Click Analyze... Linear Fit. Click File... Save as and choose a
filename of “Soln1X = 0”.
2. Record the values of regression slope (m), y‐axis value at 7 minutes (a) and the root mean
square error (RMSE). There is no need to print this graph.
3. Re‐open the “Solution1” file. Click Data... New Calculated Column. Type a Name of
Ln(Absorbance) and a Short Name of Ln(Abs). Click Functions… ln and then Variables
(Columns)... Absorbance.
4. Left click on the Y‐axis label and select Ln(Absorbance). Click Analyze... Linear Fit. Save this
graph as “Soln1X = 1”.
5. Record the required values on the Report Sheet. Print this graph in the appropriate format.
1/(Absorbance) and a Short Name of 1/Abs. In the Expression box, type “1/” and then click
Variables (Columns)... Absorbance to obtain an expression of 1 divided by absorbance.
7. Left click on the Y‐axis label and select 1/(Absorbance). Click Analyze... Linear Fit. Save this
8. Record the required values on the Report Sheet. There is no need to print this graph.
9. Compare the values of RMSE/(a) to determine the order with respect to crystal violet (the
value of X). Your data should support an order of 1. If this is not the case, consult your
instructor.
Determination of the Value of Y (order of OH ‐ ) and Rate Constant
To find the value of Y and the rate constant, k, data plots corresponding to X = 1 for Solutions 2
and 3 must be created as follows.
Ln(Absorbance) and a Short Name of Ln(Abs). Click Functions... ln (natural log) and then
Variables (Columns)... Absorbance.
2. Left click on the Y‐axis label and select Ln(Absorbance). Click Analyze... Linear Fit. Save this
3. Record the values of regression slope (m), y‐axis value at 7 minutes (a) and the root mean
square error (RMSE). There is no need to print this graph.
4. Repeat steps 1 to 3 above for Solution 3 and save your file as “Soln3X=1”.
5. Click File… New. Click Data… New Manual Column and enter a Name of [OH‐]0 and Units of
mol/L. Click Done. Click Data… New Manual Column and enter a Name of kps and click
Done. Type the hydroxide concentrations and corresponding values of kps into the table.
(See Table 13‐1 to determine the relationship between kps and the slopes of the graphs
done in steps 1 to 4 above.)
6. Click Data… New Calculated Column. Enter a Name of ln[OH‐]o. Click Functions… ln and
Variables (Columns)… [OH‐]0. Click Done.
7. Click Data… New Calculated Column. Enter a Name of ln kps. Click Functions… ln and
Variables (Columns)… kps. Click Done.
8. On the graph, left click on the Y and X axes labels to plot a graph of ln kps versus ln[OH‐]o.
Click Analyze… Linear Fit. Record the slope on the Report Sheet.
9. Click File... Save as and give a file name of “Determine Y and k”. Print the graph in the
appropriate format.
Effect of Temperature on Reaction Rate

1. Open the “Solution1temp” file. Click Data... New Calculated Column. Type a Name of
Ln(Absorbance) and a Short Name of Ln(Abs). Click Functions... ln (natural log) and then
Variables (Columns)... Absorbance.
2. Left click on the Y‐axis label and select Ln(Absorbance). Using your mouse, select (highlight)
only the data obtained after the cuvette was placed in the colorimeter. Click Analyze...
Linear Fit to fit this data. Save this graph as “Soln1temp”. Record the regression slope (m).
3. Write your measured initial, final and average temperatures and slope on the whiteboard.
4. Print this graph in the appropriate format.
5. Open a blank Logger Pro or Excel file (your choice since values are manually entered).
6. In four columns, enter initial temperature, final temperature, average temperature and
slope from the whiteboard. You should have at least 10 data points to proceed.
7. Use the functions in Logger Pro or Excel to manipulate the data and plot the required graph
to determine the activation energy. The theory section of the lab manual will help you. Print
the graph.
Grading
Prelab: _____ /2
Experiment 13 Report Sheet: Part 1 Day 1: __ /8

Kinetics of the Reaction of Part 1 Day 2: __ /10
Crystal Violet and Sodium Hydroxide Part 2: ______ /10
Name: _______________________________ Lab Day: ______________ Part 3: ______ /10
Partner’s Name: _______________________ Date: _________________ Sigfigs: ______
Units: ______
Bench #: _______ Group #: _______ TA or Instructor Initials: _______
Total: _______ /40
PART 1: DATA DAY 1
Observations:
Write observations of initial reactants, progress of reaction and final product mixture.

Temperature of solutions
Room temperature runs = ________________
High or low temperature run initial temperature = _______________
High or low temperature run final temperature = _______________

The following printed graphs are also graded in Part 1 Day 1 Data section
 Solution 1: Absorbance vs. t at room temperature (Logger Pro file “Solution1”)
 Solution 1: Absorbance vs. t at different temperature (Logger Pro file “Solution1temp”)

PART 1: DATA DAY 2 TA OR I NSTRUCTOR I NITIALS : ___________
EFFECT OF CONCENTRATION ON REACTION RATE

Table 13‐3: Determination of the Value of X
Y Value at Calculated
Solution Graph Slope (m) RMSE
7 min (a) │RMSE/(a)│
1 Abs. vs. t
1 Ln(Abs) vs. t
1 1/Abs vs. t

same values
Table 13‐4: Summary of Data for Ln(Abs) versus time Graphs
Calculated Y Value at Calculated
Solution Graph Slope (m) RMSE
[OH‐] 7 min (a) │RMSE/(a)│
1 Ln(Abs) vs. t
2 Ln(Abs) vs. t
3 Ln(Abs) vs. t

Slope of linear fit of ln kps versus ln [OH‐]o = ____________________________
y‐intercept of linear fit of ln kps versus ln [OH‐]o = ____________________________
EFFECT OF TEMPERATURE ON REACTION RATE

Record values from whiteboard in the table below. You need at least 10 sets (more is better).
Table 13‐5: Class Data for Effect of Temperature on Reaction Rate
Initial Temperature Final Temperature Average Temperature Slope of Ln(Abs) versus Time
This 1st row is your data set This 1st row is your data set This 1st row is your data set h
This 1st row is your data set

PART 2: DATA ANALYSIS
The following printed graphs are also graded in Part 1 Day 2 Data section
 Graph of Solution 1: Ln(Abs) vs. t (Logger Pro filename “Soln1X=1”) [2 points]
 Graph of ln kps versus ln [OH‐]o (Logger Pro filename “Determine Y and k”) [2 points]
 Graph to determine activation energy [2 points]

1. Use appropriate data and/or graphs to determine the order with respect to crystal violet.
Explain your answer by referring to the graphs and equations as applicable. [2 points]

2. Use appropriate data and/or graphs to determine the order with respect to hydroxide.
Explain your answer by referring to the graphs and equations as applicable. [2 points]

3. Use appropriate data and/or graphs to determine the value of the rate constant, k. Explain
your answer. [2 points]

4. Write the complete rate law for the overall reaction. [2 points]

5. Use appropriate data and/or graphs to determine the value of the activation energy, Ea.
Explain your answer. [2 points]

PART 3: QUESTIONS
1. Describe one prediction you can make about the reaction mechanism based on your
determined rate law. [1 points]

2. Use your experimentally derived rate law to calculate the initial rate of reaction for
solution 1 at room temperature. Show your work. Repeat the calculation for solutions 2 and
3 but just report the answers. Explain why the trend is observed. [3 points]

3. Use the integrated rate law to calculate the concentration of crystal violet after 15 minutes
of reaction for solution 1 at room temperature. Show your work. Repeat the calculation for
solutions 2 and 3 and report the answers. Explain why the trend is observed. [3 points]

4. Discuss at least three sources of error in this experiment. You should not give human errors
such as pipetting error, etc. [3 points]

REPORT (INDIVIDUAL): Complete the following and staple together in the order given:

 Report Sheets from the laboratory experiment
 Graph of Solution 1: Absorbance vs. t at room temperature (Logger Pro file “Solution1”)
 Graph of Solution 1: Absorbance vs. t at different temperature (Logger Pro file
“Solution1temp”)
 Graph of Solution 1: Ln(Abs) vs. t (Logger Pro filename is “Soln1X=1”)
 Graph of ln kps versus ln [OH‐]o (Logger Pro filename is “Determine Y and k”)
 Graph to determine activation energy

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Experiment

Monitoring the Reaction by Colorimetry

EXPERIMENT 13A PROCEDURE DAY 1

Effect of Concentration on Reaction Rate

Effect of Temperature on Reaction Rate

PROCEDURE DAY 2: DATA ANALYSIS

EFFECT OF CONCENTRATION ON REACTION RATE

Effect of Temperature on Reaction Rate

Experiment 13 Report Sheet: Part 1 Day 1: __ /8

Name: _______________________ Lab Day: Part 3: /10

Partner’s Name: _____________ Date: _ Sigfigs:

EFFECT OF CONCENTRATION ON REACTION RATE

EFFECT OF TEMPERATURE ON REACTION RATE

REPORT (INDIVIDUAL): Complete the following and staple together in the order given:

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