Walsh Kang

Dr. Lowery
AP Chemistry P1
26 November 2014
Kinetics of Crystal Violet Fading
II. Objective:
The purpose of this lab is to use spectroscopy and graphical analysis to
determine the rate law for the reaction of crystal violet with sodium hydroxide.
III. Background:
Crystal violet is a violet-colored compound that loses its color when in a
strong basic solution. The crystal violet cation (CV+) combines with hydroxide ions
to form CVOH, a neutral colorless product. The first reaction is shown here:
CV+ + OH- CVOH
The general rate law form of this reaction is shown here:
Rate = k[CV+]n[OH-]m
The variables n and m are the order of the reaction with respect to each
reactant and k is the rate constant at a specific temperature. If there is a huge
excess of OH-, then the concentration of OH- will fold into the rate constant,
changing the rate law as so:
Rate = k[CV+]n, where k = k[OH-]m
This is a pseudo rate law because it is a simpler version of the actual rate
law.
A Beers Law curve must be made in order to convert the absorbances
measured from the spectrophotometer into concentrations. The general
relationship between concentration and absorbance is this:
A = abc
A is the absorbance, a is the molar absorptivity coefficient, b is the path
length in centimeters, and c is the concentration. Beers Law is used to track the
concentration of CV+ as the reaction progresses in a test tube with the absorbance
being measured.

After finding the concentrations at certain times of the reaction of CV+ and
OH-, graphical analysis can be used, because zero, first, and second order
derivative rate laws can be graphed: zero order ([CV+] vs. time), first order
(ln[CV+] vs. time), or second order (1/[CV+] vs. time). If the data shows a straight
line, then the reaction is that order.
IV. Materials:
Materials for part 1 (constructing Beers Law curve)
-

Crystal violet solution, 25 M (2.5 * 10-5 M), 50 mL

Sodium hydroxide solution, 0.02 M, 30 mL
Distilled water
Beaker, borosilicate, 50 mL
Spectrophotometer
Test tubes
Pipets, serological, 10-mL
Pipet bulb filler
5 disposable pipets
Stirring rod
Permanent marker

Materials for part 2 (graphical analysis of rxn. of CV+ and OH-)

-

Crystal violet solution, 25 M (2.5 * 10-5 M), 50 mL

Sodium hydroxide solution, 0.02 M, 30 mL
Spectrophotometer
1 test tube, 13*100mm
2 pipets, serological, 10-mL
Pipet bulb filler
Stirring rod
Stopwatch
1 Kimwipe
Permanent marker

V. Safety Issues:
For both parts of the experiment, sodium hydroxide solution is irritating to
eyes and skin. Crystal violet will stain clothes and skin. Caution should be used
with these solutions. Goggles, gloves, and aprons should be worn. Chemicals
should be avoided. All lab safety rules should be adhered to.
VI. Procedure:
Procedure for obtaining a calibration curve for crystal violet
1. Turn on the spectrophotometer and allow it to warm up for 15-20 minutes
before. Adjust the wavelength setting to 540 nm.

2. Obtain five test tubes and label them with a permanent marker: A, B, C, D,
and E. Using one serological pipet and pipet bulb filler, fill test tube A with
9.0 mL of water, and using the other serological pipet, fill test tube A with
1.0 mL of the stock solution of crystal violet.
3. Making sure to use each pipet for its own respective solution, construct the
other four solutions: 8.0 mL of water and 2.0 mL of stock solution in test
tube B, 7.0 mL of water and 3.0 mL of stock solution in test tube C, 6.0 mL of
water and 4.0 mL of stock solution in test tube D, and 5.0 ml of both water
and stock solution in test tube E. Use the stirring rod to mix all of these
solutions, making sure to dry the stirring rod after each stir.
4. Take one test tube, 13 by 100mm, and make a small line on the top of the
tube, to mark where the tube will be lined up in the spectrophotometer. Fill
the tube three quarters of the way full with distilled water.
5. Put the test tube into the spectrophotometer and adjust the percent
transmittance to 100 percent.
6. Take the test tube out and fill it of the way full with mixture A using a
disposable pipet. Wipe the exterior of the tube with the Kimwipe and place
the test tube in the spectrophotometer, making sure to line up the drawn
line with the mark in the spectrophotometer.
7. Set the spectrophotometer to absorbance and record the absorbance of
mixture A.
8. Take the test tube out and pour out mixture A. With a different disposable
pipet, take some of mixture B and rinse out the test tube. Then, pipet
mixture B into the test tube.
9. Repeat steps 6-8 with all of the mixtures A-E, by rinsing with the next
mixture and recording the absorbances.

Procedure for obtaining the graphs needed to find the order of the reaction with
respect to CV+:
1. Using a serological pipet with a bulb filler, pipet 830 mL of .02 M naOH into
the 13 by 100 mm test tube. Make a mark on the test tube with the
permanent marker. Wipe the test tube with the Kimwipe.
2. Set the wavelength of the spectrophotometer to 540 nm and place the test
tube with 8.0 mL of .02 M NaOH in the spectrophotometer set for
transmittance by lining up the marks.
3. Adjust the percent transmittance to 100, then take the test tube out of the
spectrophotometer.
4. Empty the test tube and pipet 4.0 mL of the 25 M crystal violet into the test
tube with the 4.0 mL of .02 M Naoh, starting the stopwatch as soon as the
crystal violet is pipetted.
5. Use the stirring rod to mix the crystal violet and NaOH, wipe the test tube,
and put the test tube into the spectrophotometer by lining up the marks.

6. Flip the switch of the spectrophotometer to absorbance. Steps 5-7 should

have happened in less than 20 sec.
7. Record the absorbance value every 20 seconds for 20 minutes.

VII. Results:
Data Table 1 (measured with a wavelength of 540 nm)
Mixt
ure

Absorba
nce

Concentratio
n of CV+
(M)
2.5

5.0

.24

7.5

.34

10.0

.48

12.5

.58

.12

Graph 1

Abs. vs. [CV+] (M)

A
b
s
o
r
b
a
n
c
e

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
2

8
[CV+] (M)

Y = .0464x + .004, r = .9988

10

12

14

Data Table 2 (measured with a wavelength of 540 nm)

***attach data from Excel***

Graphs 2-4
***attach data from Excel and write in r-values***
Calculation 1 (determination of the order with respect to CV+)

Calculation 2 (determination of the order with respect to OH-)

Final rate law

Guided inquiry design and procedure A. 1-4 and B. 1-4

VIII. Conclusion:
The objective of this experiment was to find the rate law of the reaction
between crystal violet and sodium hydroxide. This was done by first constructing a
Beers law curve to have the ability to convert absorbance into concentration, then
measuring the change in absorbance (inherently concentration) of crystal violet as
the reaction commenced. The rate law was determined to be Rate = k[CV+][OH-] 3,
an overall fourth order reaction. With a fourth order reaction being unlikely, there
are three sources of error that could have contributed to this absurd order. The
three errors are a lack of agitation in the test tube containing CV+ and OH-, having
too little CV+ in the solutions used to construct the Beers law curve, and not
pipetting enough CV+ into the test tube with sodium hydroxide.
The first error is not having agitation in the test tube that contains the
reaction of CV+ and OH-. This would change the order of the reaction. Without any
agitation, the CV+ and OH- cannot react as much because the molecules of CV+ will
not collide with as many OH- ions. This reduces the rate of the reaction because
there are not as many effective collisions or frequency of collisions and so since the
rate decreased, the concentration will be higher at a certain time because there is
more CV+ left than there should be. The slope of [CV+] vs. time will be much
shallower because the concentration wont change as much. That means that the
slope of ln[CV+] vs. time and 1/[CV+] vs. time will also be shallower. The amount
the points change cannot be determined because the magnitude of the change in

slopes cannot be determined exactly. The r-values may or may not change, but they
most likely will. This might force an order to be preferred over another order. So the
lack of agitation in the test tube will change the order of the reaction. A way to
prevent this error is to use the stirring rod and mix the solution well.
The second error is having too little CV+ in the solutions used to construct
the Beers law curve. This is a decrease in concentration. According to the equation
A = abc, concentration and absorbance are directly proportional, so a decrease in
concentration would lead to a decrease in absorbance. The slope and y-intercept of
the Beers law curve will change, depending on how lacking the CV+ is. Yet if all of
the solutions lack the same amount of CV+, only the y-intercept will decrease, with
the slope staying the same. So now, for any absorbance, the corresponding
concentration will be larger-than-normal because you are subtracting a smaller bvalue from the absorbance to calculate the concentration. There would be an
increase in the values for ln[CV+] and a decrease in the values for 1/[CV+]. All of
these changes in values would be constant and so the shapes of the graphs would
not change. Therefore the order would be determined just the same. This error
would not have an effect on the determination of the order of the reaction with
respect to either reactant. A way to avoid this source of error would be to properly
pipet the CV+ and to make sure that the dead space or lack of it is observed.
The third error is not pipetting enough CV+ into the test tube with sodium
hydroxide. According to the rate law, a decrease in concentration of CV+ (which is
what happens when less CV+ is pipetted into the test tube), will lead to a decrease
in rate. So now the absorbances do not correlate with the right times. Since the rate
decreased, the concentration will be higher at a certain time because there is more
CV+ left than there should be. The difference in CV+ remaining is more evident as
time progresses. The slopes of the graphs of [CV+] vs. time, ln[CV+] vs. time, and
1/[CV+] vs. time will be shallower, possibly changing the r-values. This will possibly
change the determination of the order. Depending on what the final graphs look like,
the order might look like zero, first, or second. This is how not pipetting enough CV+
into the test tube with sodium hydroxide affects the determination of the order of
the rate law. A way to avoid this error would be to properly pipet and to make sure
that the dead space or lack of it is observed.