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What is the Rate Law for the Crystal Violet Reaction?
3/27-4/3/2014
Section 10th
TA: Jinwei Zhang
Group 6
Daylin Morgan
Ahmed Alsharif
Shili Tong
Chang Chuan
Introduction
The main goal of this experiment was about observing the
reaction between crystal violet and sodium hydroxide, CV+ +
OH- -> CVOH. The objectives of this experiment are to monitor
the absorbance of the crystal violet solution as a function of
time, and determining the order of the reaction with respect to
CV+. The pseudo rate constant k’ in this reaction is derived
from the knowledge that OH- and the rate constant can be
combined to a single constant. The Beer’s Law relationship
between absorbance and concentration for CV+ is used to
calculate the concentration in a solution given the Absorbance
and a calculated constant. The half-life for this reaction with
respect to CV+ and the rate law for this reactionare derived
from total data.
Materials & Procedure
Materials
2.5*10-5M CV+(aq)
2.5*10-5 M OH-(aq)
Volumetric measuring equipment
Beaker
Cuvette
Stirring Rod
Spectrophotometer
Each student in a group will measure kinetics of the reaction at
different concentration of sodium hydroxide. Before starting
kinetic measurements, you should measure the spectrum of the
crystal violet in the aqueous solution and establish the
wavelength suitable for absorption measurements. Of course,
this wavelength is the same for the whole class, so there is no
reason to establish it once and once again.
Created 4 different solution of H2O and Crystal Violet at
specific concentration. Measured the absorbance of each of
these concentration using spectrophotometer and noted
absorbance.
Graphed the absorbance vs. concentration, and found line of
best-fit with an intercept of 0 to find value of m= εb.
Prepared spectrophotometer for kinetics measurements (separate
instructions will be provided for each group).
Pour 10 mL of NaOH solution into 10 mL beaker. CAUTION:
Sodium hydroxide solution is caustic. Avoid spilling it on your
skin or clothing.
Pour 10 mL of 2.0 X 10-5 M crystal violet solution. CAUTION:
Crystal violet is a biological stain. Avoid spilling it on your
skin or clothing.
Initiated the reaction, simultaneously poured the 5-mL portions
of crystal violet and sodium hydroxide into a 25-mL beaker and
stirred the reaction mixture. Rinsed the cuvette with ~1-mL
amounts of the reaction mixture and then filled it 3/4 full.
Placed the cuvette in the cuvette slot of the spectrophotometer,
and clicked "Collect" button. The program collected the
absorbance data.
Analyzed the data graphically to decide if the reaction is zero,
first, or second order with respect to crystal violet.
Results
Conc.(M)
A
0.000125
1.609
0.0001
1.244
0.000075
1.019
0.00005
0.53
*Measured with λmax= 600nm
Determining Beer-Lambert’s Law
A=εbC
Using the linear-fit line above εb was determined to equal
12695.
Determining the order wrt [CV+]:
To find molarity of CV+ used Beer-Lambert’s Law and
value for εb found above.
A=εbC
1.331=12695C
C=1.331/12695
C=1.05*10-4
Below is the graph comparing the concentration vs. time.
Below is the graph comparing ln(conc.) vs. time.
Below is the graph comparing 1/conc. vs. time.
Given the graphs and linear regressions above it was determined
that the Crystal Violet undergoes a first order reaction.
The psuedo rate constant or k’=|slope| is k’=.0066.
At this psuedo constant the temperature is room temperature,
and the OH- in excess and considered to be constant.
Half-life:
Using the equation t1/2 = t * ln(2)/ln(N0/Nt).
The half-life was estimated to be t1/2 = 200 * ln(2)/ln(1.05*10-
4/5.7*10-5)
t1/2=226.923s
The rate law expression for the reaction is Rate=.0066[CV+].
Discussion
For this reaction the λmax was 600nm. This was calculated
using the spectrophotometer and an aqueous solution of CV+.In
regards to this experiment it was necessary to use the Beer-
Lambert’s law to determine the concentration of the solutions as
it reacted. Since there is no way to measure the concentration
accurately every 2 seconds over a long interval the absorbance
rate can be used to calculate what the concentration is at any
given point in time. Absorbance can’t be used to calculate the
rate constant because the values would not be correct with
respect to OH- concentrations. The rate constant and pseudo
rate constant are affected by things like the temperature of a
given system. This system was performed under the condition of
room temperature. The rate of a reaction will increase with the
concentrations of either CV+ or OH-. Since crystal violet is a
first order reaction doubling it for instance should double the
rate. A common error for any experiment involving the
spectrophotometer could be a cuvette that is not clean on the
smooth sides, or even inserted the wrong way. These errors
would substantially affect the absorbance measurements.
Another error might be spilling solution in the
spectrophotometer itself. The errors can be minimized by
executing caution and consideration for the equipment during
when in lab.
Conclusion
The goal of this experiment was to observe the reaction kinetics
between crystal violet and an excess of sodium hydroxide to
determine the order of the reaction with respect to crystal
violet. Once the proper wavelength has been chosen for the
crystal violet and the spectrometer has been calibrated, the
absorbance is measured. The rate law for this reaction as listed
above is .0066[CV+]. Beer-Lamberts law states that absorbance
is proportional to concentration, which is significant in this
experiment because it allows one to plot absorbance vs
concentration to find the constant needed. With this in mind, the
order with respect to crystal violet can be determined by the
absorbance versus time plot. Which was found to be a first
order reaction with respect to CV+.
Appendix
T(s)
A
A/eb=C
ln[CV]
1/CV
T(s)
A
A/eb=C
ln[CV]
1/CV
0
1.331
1.05E-04
-9.16303
9.54E+03
102
0.712
5.61E-05
-9.78864
1.78E+04
2
1.311
1.03E-04
-9.17817
9.68E+03
104
0.701
5.52E-05
-9.80421
1.81E+04
4
1.301
1.02E-04
-9.18583
9.76E+03
106
0.691
5.44E-05
-9.81858
1.84E+04
6
1.288
1.01E-04
-9.19587
9.86E+03
108
0.681
5.36E-05
-9.83316
1.86E+04
8
1.274
1.00E-04
-9.2068
9.96E+03
110
0.672
5.29E-05
-9.84646
1.89E+04
10
1.261
9.93E-05
-9.21706
1.01E+04
112
0.662
5.21E-05
-9.86145
1.92E+04
12
1.247
9.82E-05
-9.22822
1.02E+04
114
0.653
5.14E-05
-9.87514
1.94E+04
14
1.231
9.7E-05
-9.24114
1.03E+04
116
0.644
5.07E-05
-9.88902
1.97E+04
16
1.218
9.59E-05
-9.25175
1.04E+04
118
0.635
5E-05
-9.90309
2.00E+04
18
1.208
9.52E-05
-9.26
1.05E+04
120
0.628
4.95E-05
-9.91418
2.02E+04
20
1.195
9.41E-05
-9.27082
1.06E+04
122
0.62
4.88E-05
-9.927
2.05E+04
22
1.184
9.33E-05
-9.28006
1.07E+04
124
0.611
4.81E-05
-9.94162
2.08E+04
24
1.173
9.24E-05
-9.2894
1.08E+04
126
0.603
4.75E-05
-9.9548
2.11E+04
26
1.159
9.13E-05
-9.30141
1.10E+04
128
0.595
4.69E-05
-9.96816
2.13E+04
28
1.145
9.02E-05
-9.31356
1.11E+04
130
0.586
4.62E-05
-9.9834
2.17E+04
30
1.134
8.93E-05
-9.32321
1.12E+04
132
0.58
4.57E-05
-9.99369
2.19E+04
32
1.123
8.85E-05
-9.33296
1.13E+04
134
0.573
4.51E-05
-10.0058
2.22E+04
34
1.11
8.74E-05
-9.3446
1.14E+04
136
0.565
4.45E-05
-10.0199
2.25E+04
36
1.098
8.65E-05
-9.35547
1.16E+04
138
0.558
4.4E-05
-10.0324
2.28E+04
38
1.087
8.56E-05
-9.36554
1.17E+04
140
0.551
4.34E-05
-10.045
2.30E+04
40
1.072
8.44E-05
-9.37944
1.18E+04
142
0.543
4.28E-05
-10.0596
2.34E+04
42
1.059
8.34E-05
-9.39164
1.20E+04
144
0.535
4.21E-05
-10.0745
2.37E+04
44
1.045
8.23E-05
-9.40495
1.21E+04
146
0.527
4.15E-05
-10.0895
2.41E+04
46
1.031
8.12E-05
-9.41843
1.23E+04
148
0.52
4.1E-05
-10.1029
2.44E+04
48
1.018
8.02E-05
-9.43112
1.25E+04
150
0.513
4.04E-05
-10.1164
2.47E+04
50
1.006
7.92E-05
-9.44298
1.26E+04
152
0.506
3.99E-05
-10.1302
2.51E+04
52
0.993
7.82E-05
-9.45599
1.28E+04
154
0.5
3.94E-05
-10.1421
2.54E+04
54
0.98
7.72E-05
-9.46917
1.30E+04
156
0.493
3.88E-05
-10.1562
2.58E+04
56
0.967
7.62E-05
-9.48252
1.31E+04
158
0.489
3.85E-05
-10.1644
2.60E+04
58
0.957
7.54E-05
-9.49292
1.33E+04
160
0.482
3.8E-05
-10.1788
2.63E+04
60
0.945
7.44E-05
-9.50553
1.34E+04
162
0.475
3.74E-05
-10.1934
2.67E+04
62
0.932
7.34E-05
-9.51939
1.36E+04
164
0.469
3.69E-05
-10.2061
2.71E+04
64
0.92
7.25E-05
-9.53235
1.38E+04
166
0.462
3.64E-05
-10.2212
2.75E+04
66
0.909
7.16E-05
-9.54437
1.40E+04
168
0.456
3.59E-05
-10.2342
2.78E+04
68
0.898
7.07E-05
-9.55655
1.41E+04
170
0.449
3.54E-05
-10.2497
2.83E+04
70
0.885
6.97E-05
-9.57113
1.43E+04
172
0.444
3.5E-05
-10.2609
2.86E+04
72
0.875
6.89E-05
-9.58249
1.45E+04
174
0.438
3.45E-05
-10.2745
2.90E+04
74
0.863
6.8E-05
-9.5963
1.47E+04
176
0.434
3.42E-05
-10.2837
2.93E+04
76
0.851
6.7E-05
-9.61031
1.49E+04
178
0.428
3.37E-05
-10.2976
2.97E+04
78
0.842
6.63E-05
-9.62094
1.51E+04
180
0.422
3.32E-05
-10.3117
3.01E+04
80
0.831
6.55E-05
-9.63409
1.53E+04
182
0.417
3.28E-05
-10.3236
3.04E+04
82
0.819
6.45E-05
-9.64863
1.55E+04
184
0.412
3.25E-05
-10.3357
3.08E+04
84
0.811
6.39E-05
-9.65845
1.57E+04
186
0.405
3.19E-05
-10.3528
3.13E+04
86
0.8
6.3E-05
-9.67211
1.59E+04
188
0.4
3.15E-05
-10.3653
3.17E+04
88
0.789
6.22E-05
-9.68595
1.61E+04
190
0.394
3.1E-05
-10.3804
3.22E+04
90
0.779
6.14E-05
-9.69871
1.63E+04
192
0.388
3.06E-05
-10.3957
3.27E+04
92
0.769
6.06E-05
-9.71163
1.65E+04
194
0.383
3.02E-05
-10.4087
3.31E+04
94
0.758
5.97E-05
-9.72604
1.67E+04
196
0.378
2.98E-05
-10.4218
3.36E+04
96
0.747
5.88E-05
-9.74065
1.70E+04
198
0.372
2.93E-05
-10.4378
3.41E+04
98
0.737
5.81E-05
-9.75413
1.72E+04
200
0.367
2.89E-05
-10.4514
3.46E+04
100
0.723
5.7E-05
-9.77331
1.76E+04
Rate Law for the Crystal Violet Reaction

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