Concentrations of Crystal Violet as it Reacts with Sodium Hydroxide

Laura Glastra
glastrlk@plu.edu
Lab Partner: Alex Ronero
General Chemistry 116

Department of Chemistry,
Pacific Lutheran University,
Tacoma, WA, 98447 USA
Submitted for grading: March 24, 2016

Abstract: In this experiment the values of absorbance are recorded spectrometrically over time
as CV reacts with NaOH to become a colorless liquid. The absorbance decreases over time as the
color of the violet dissipates because less light is being absorbed by the photons as they pass
through the cuvette. The rates of reaction were greatest when the reaction occurred in the highest
temperature and lowest when the reaction took place at room temperature. Activation energy
remained constant as it is independent of temperature.

Introduction

The reaction of crystal violet (C25H30N3) and sodium hydroxide (NaOH) can be written as
C25H30N3+ + OH- C25H31N3O.1 The purpose of this experiment is to determine the reaction rate
of crystal violet (CV) and NaOH. Rate of reaction determines the speed at which reactants
(C25H30N3+ and OH-) form products (C25H31N3O). Increasing the concentration of reactant or
increasing the temperature of a system both correspond to faster rates of reaction. In this
experiment, the reaction rate is calculated at three different temperatures. Higher temperatures
are hypothesized to have quicker reaction rates. This is due to particles of reactants colliding
more quickly and frequently since the kinetic energy of the system has increased.
.
Rate laws are experimentally determined values that relate reaction rates to concentration of
reactants. A pseudo-rate law is treats a reaction as though it is first order when the concentration
of one reactant is in such excess that the amount used in the reaction is so minor in relative to the
amount of other reactant. In this experiment, hydroxide is in excess and crystal violet is treated
as the reactant that is first order. To determine concentration of a substance at a specific time, or
how long it will take for a concentration to reach a certain level the integrated rate law for a first
order reaction is used. Integrating the rate law of a second order reaction can provide values of
concentration after a certain amount of time elapses, the amount of time it takes to reach a certain
concentration, as well as the rate constant. Rate constants are related to the number of collisions
and the activation energy of a given reaction through the Arrhenius equation. This provides
1 Munro, A. M. PLU Sakai CHEM 116 Course Support Website Handout : Lab 1, A Kinetics Study; Bleaching
Crystal Violet with NaOH. From http://sakai.plu.edu/, accessed 2/23/2016

insight to the molecular movements in a reaction and the amount of energy in the system. The
last equation that will be used for calculations in this experiment is Beers Law. Beers Law
represents the concentration of a substance through the measured absorbance value.

Experimental
Materials
A Vernier visible spectrometer was used to measure absorbance and wavelength of the solutions.2
The cuvettes used with the spectrometers were made of clear, colorless plastic. Six large test
tubes (25 x 150 mm) were used to contain CV and NaOH solutions. To thermally equilibrate
solutions, an 800 mL beaker filled with water was used for measuring solutions at room
temperature. Two separate water baths were heated to thermally equilibrate solutions at higher
temperatures.

Preparation of Compounds
Three test tubes were filled with 5 mL of 3.0 x 10-4 M CV solution while three separate tubes
were filled with 25 mL of 1.99 x 10-2 M NaOH. One test tube containing each solution was
placed into three waterbaths at different temperatures. The water bath at room temperature was
measured to be 22.6 , the second bath was measured as 26.3 , and the third as 38.9 . The
2 Munro, A. M. PLU Sakai CHEM 116 Course Support Website Handout : Lab 1, A Kinetics Study; Bleaching
Crystal Violet with NaOH. From http://sakai.plu.edu/, accessed 2/23/2016

test tubes in each bath thermally equilibrated for a minimum of 15 minutes. After 26 minutes, the
solutions in the room temperature water bath were mixed. The test tube containing the mixed
solution was immediately placed back into the water bath so the reaction continued to take place
at the same 22.6 . The absorbance and wavelength measured spectrometrically seven minutes
after mixing. The maximum absorbance and corresponding wavelength were recorded.
Following measurements of the other solutions were recorded at the wavelength where the
highest absorbance was found for the first measurement. The absorbance of solution in the
second bath at 26.3 were taken approximately seven later, but absorbance of solution in third
bath at 38.9 were recorded two minutes after mixing. Measurements of absorbance were
recorded for all three solutions every two minutes. The cuvette was thoroughly rinsed with
deionized water and dried between measurements of different solutions.

Hazards/Safety Information
It should be noted that NaOH is corrosive to skin and metals. CV may cause serious eye damage,
is a Category 2 carcinogen, and has acute oral toxicity. Both chemicals have acute aquatic
toxicity and should be disposed of properly as chemical waste.3

Results & Discussion

3 "Sigma-Aldrich: Analytical, Biology, Chemistry & Materials Science Products and Services." Sigma-Aldrich.
N.p., n.d. Web. 16 Mar. 2016.

As the amount of time elapses from the start of reaction (when CV and NaOH are mixed), the
absorbance values recorded decrease. The highest absorbance for each solution is the first
recorded measurement. For the solution at 22.6 , the highest absorbance occurred seven
minutes after the start of reaction at 0.958, with the lowest value recorded 23 minutes after the
start of reaction at 0.234 (Table 1). At 26.3 , the highest absorbance value was 1.781 with the
low at 0.290 taken two minutes and 18 minutes respectively after the start of reaction (Table 2).
The reaction at 38.9 had a high of 1.860 one minute after the start of reaction, and low of
0.343 10 minutes after the start of reaction for absorbance (Table 3). The absorbance values
decrease because the dark violet color characteristic to CV is transforming into a colorless liquid
because of the reaction with NaOH. The violet color of CV is due to the chemical structure of the
molecule, which has carbon as its central atom. The carbon is stabilized through double bonds
with the surrounding atoms, but when OH- is introduced it bonds with the central carbon, which
breaks the bond between the carbon and surrounding atoms. The breaking of this bond is
responsible for the transformation of CV into a colorless liquid. As the bonds break and the
solution becomes colorless, the absorbance decreases due to more photons being reflected,
instead of absorbed, through the cuvette.4, 5

The highest absorbance measured takes place in the environment with the highest thermal
energy. This is seen in the solution reacted at 38.9 while the lowest original absorbance
occurred at 22.6 . The absorbance values are higher for reactions that occur in higher
4 Brown, Theodore L., H. Eugene LeMay, and Bruce Edward. Bursten. Chemistry: The Central Science. Upper
Saddle River, NJ: Prentice Hall, 2000. Print.
5 Ghosh, Soumen, Satyajit Mondal, Sibani Das, and Rathin Biswas. "Spectroscopic Investigation of Interaction
between Crystal Violet and Various Surfactants (cationic, Anionic, Nonionic and Gemini) in Aqueous Solution."
Spectroscopic Investigation of Interaction between Crystal Violet and Various Surfactants (cationic, Anionic,
Nonionic and Gemini) in Aqueous Solution. Fluid Phase Equilibria, 25 Oct. 2012. Web. 23 Mar. 2016.

temperatures because the molecules are colliding more frequently. Kinetic-molecular theory
supports that the reaction is able to take place more quickly due to molecules colliding more
frequently and forcefully in a given time period.6

Through Beers Law, it is possible to directly relate the absorbance and concentration of solution
since the length of the cell the light travels through is a constant and all measurements were
recorded at the same wavelength. The relation of time to concentration is therefore shown in
Figures 1-3 as time versus 1/A. This represents the rate of the reaction as it is a second order
reaction, and has the rate constant as the slope of the line. To show the actual concentrations of
the solution at any given time, ln(A) versus time is graphed as shown in Figures 4-6. The slope is
negative and represents the rate constant of a reaction for first order reactions. The graph of ln[A]
versus time also provides information to find the original concentration of the solution at time
zero. This reaction can be graphed as first because the values are calculated with respect to the
pseudo-rate constant in relation to the concentration of CV. This is possible because the change
in NaOH concentration used through the reaction is so minor given the large amount of it present
in solution. To represent the amount of collisions between the two compounds, the frequency
factor was calculated to be 108,550 M-1s-1. The amount of energy required to activate the reaction
was also calculated and found to be 0.26 M-1s-1.

Table 1. Values Recorded at 22.6

t [sec]
Abs
ln(Abs)
1/Abs
420
0.958
-0.042907501
551
0.728
-0.317454231

1.043841336
1.373626374

6 Brown, Theodore L., H. Eugene LeMay, and Bruce Edward. Bursten. Chemistry: The Central Science. Upper
Saddle River, NJ: Prentice Hall, 2000. Print.

660
780
900
1020
1140
1260
1380

0.583
0.465
0.383
0.323
0.283
0.253
0.234

-0.539568093
-0.765717873
-0.95972029
-1.130102956
-1.262308381
-1.37436579
-1.452434164

1.715265866
2.150537634
2.610966057
3.095975232
3.533568905
3.95256917
4.273504274

Table 2. Values Recorded at 26.3

t [sec]

Abs
0 na
120
240
360
480
600
720
840
960
1080

26.3
ln(Abs)
1.781
1.388
1.073
0.813
0.627
0.495
0.401
0.338
0.29

1/Abs

0.577175004
0.327863862
0.070458464
-0.207024169
-0.466808738
-0.703197516
-0.913793852
-1.084709383
-1.237874356

0.561482313
0.720461095
0.931966449
1.2300123
1.594896332
2.02020202
2.493765586
2.958579882
3.448275862

Table 3. Values Recorded at 38.9

t [sec]

38.9
ln(Abs)

Abs
60
120
180
240
300
360
420
480
540
600

1.86
1.497
1.19
0.963
0.783
0.643
0.532
0.451
0.391
0.343

0.620576488
0.403463105
0.173953307
-0.037701867
-0.244622583
-0.441610555
-0.63111179
-0.79628794
-0.939047719
-1.070024832

1/Abs
0.537634409
0.668002672
0.840336135
1.038421599
1.277139208
1.555209953
1.879699248
2.2172949
2.557544757
2.915451895

Figure 1. Concentration of CV over time.

Figure 1. A plot of 1/A versus time to represent changes in concentration as the reaction
proceeds.
Figure 2. Concentration of CV over time.

Figure 3. Plot representing the concentration of CV over time as the reaction proceeds.

Figure 3. A plot of 1/A over time to represent the concentration over time.
Figure 4.

Figure 4. A plot of ln(A) vs. T for the reaction of crystal violet and sodium hydroxide as the
reaction takes place at room temperature.
Figure 5.

Figure 4. A plot of ln(A) vs. T for the reaction of crystal violet and sodium hydroxide as the
reaction takes place at 26.3 .
Figure 6.

Figure 4. A plot of ln(A) vs. T for the reaction of crystal violet and sodium hydroxide as the
reaction takes place at 38.9 .
It is possible that human sources of error occurred in this experiment. One source of error could
be that different amounts of time elapsed between measurements. Though the measurements

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were recorded approximately every two minutes, they were not recorded at exactly two minutes
apart. It is crucial that the original value of wavelength at the highest absorbance is recorded
because if not it will greatly affect the calculations.

Conclusion
In this experiment the values of absorbance are recorded over time as CV reacts with NaOH to
become a colorless liquid. The absorbance decreases over time as the color of the violet
dissipates because less light is being absorbed by the photons as they pass through the cuvette.
One of the key values calculated was the rate of reaction, which were greatest when the reaction
occurred in the highest temperature and lowest when the reaction took place at room
temperature. The concentrations of the solutions were compared against time through the use of
Beers Law, which makes it possible to use the concentration directly as absorbance, and the
Arrhenius equation, which relates the rate constant to the number of collisions occurring and the
activation energy. The reactions at the highest temperatures had the highest number of collisions
over a given time interval, but the activation energy remained as it is independent of temperature.

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References
1. Brown, Theodore L., H. Eugene LeMay, and Bruce Edward. Bursten. Chemistry: The Central
Science. Upper Saddle River, NJ: Prentice Hall, 2000. Print.
2. Ghosh, Soumen, Satyajit Mondal, Sibani Das, and Rathin Biswas. "Spectroscopic
Investigation of Interaction between Crystal Violet and Various Surfactants (cationic, Anionic,
Nonionic and Gemini) in Aqueous Solution." Spectroscopic Investigation of Interaction between
Crystal Violet and Various Surfactants (cationic, Anionic, Nonionic and Gemini) in Aqueous
Solution. Fluid Phase Equilibria, 25 Oct. 2012. Web. 23 Mar. 2016.
3. Munro, A. M. PLU Sakai CHEM 116 Course Support Website Handout : Lab 1, A Kinetics
Study; Bleaching Crystal Violet with NaOH. From http://sakai.plu.edu/, accessed 2/23/2016
4. "Sigma-Aldrich: Analytical, Biology, Chemistry & Materials Science Products and Services."
Sigma-Aldrich. N.p., n.d. Web. 16 Mar. 2016.

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