Chemistry 315

Experiment 04:
Kinetics of the cis-trans Isomerization
of 4-Anilino-4’-nitroazobenzene
Victoria Wisniewski

School of Chemical Sciences, 505 S. Mathews Ave., Urbana, IL 61801

vjw2@illinois.edu

Lab partner: Sam Smith, Kean Zhu

Lab section: AB2, Tuesday PM

Major: Chemical Engineering

Date of lab work: 10/01/2019

Due date of report: 10/08/2019

Keywords: FLASH PHOTOLYSIS, UV-VIS SPECTROSCOPY, ISOMERIZATION,

AZOBENZENE, BEER’S LAW

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Experimental Details
The water pump was connected to an outlet, and the temperature was set to 30 °C.
The Cary Agilent 60 UV-Vis was calibrated for a wavelength range of 600 nm to 300
nm. A baseline spectrum was taken by using a cuvette filled with cyclohexane. Next, a
drop of orange solution was added to the cyclohexane, and the maximum absorbance was
recorded to be 0.099. This gave a λmax of 435 nm.

Kinetics was open on the computer, and the following parameters were set:
wavelength = 435; cycle = 0.1 min; stop = 5 min. The cuvette was placed into the
spectrophotometer and Start was selected. At 30 seconds, the cuvette was quickly taken
out, and a camera flash was used to flash it. The cuvette was immediently replaced back
into the spectrophotometer, and the test was run until the total run time was 5 minutes.

This test was repeated, and then the temperature was changed to 40 °C. After two
minutes of waiting to ensure that the temperature rose. Then, the experiment was run
twice. This process was repeated for 50 °C and 60 °C. All files were saved as Excel files
and the experiment was cleaned up. 1

Data and Results

The absorbance maximums were found for each data set. The absorbance
maximums were found near when the flash was done, or appoximetely 30 seconds,
expect for three data points which will be discussed about later. The maxiumums can be
found in the following table.

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Table 1. Values of maximum absorbance for every reaction.

Trial # Temperature (C) Time (min) Absorbance

30 0.601 0.121815
40 5.001 0.128146
1
50 0.501 0.132063
60 4.801 0.133279
30 0.501 0.118992

2 40 0.501 0.12986

50 0.501 0.132378

60 4.801 0.135061

These maximums were essential to find as it can be used in the following expression,
which then gives the rate constant of the reaction.

ln ( A ∞− At )=−kt + ln ⁡( A ∞− A0 ) (1)

Each reaction was then graphed using the above equation, as can be seen in the figures in
the supplementary section. The slopes of each trendline are the rate constants of the
reaction. The results can be found the Table 2.

Table 2. Values of maximum absorbance for every reaction.

Temperature (C) Rate Constant Average Rate

3
 (sec-1) Constant (sec-1)
30 0.0043
30 0.0040
0.00415
40 0.0091
40 0.0099
0.0095
50 0.0143
50 0.0151
0.0147
60 0.0243
60 0.0181
0.0424

The Arrhenius equation can be used to determine the activation energy and the enthalpy
of entrophy of activation. This equation is known below:

Ea
ln ( k )=ln ( A ) − (2)
RT

ln(kavg) vs (1/T)
0

-1

-2
ln(Kavg)

-3
f(x) = − 7463.85 x + 19.11
-4 R² = 0.97

-5

-6
0 0 0 0 0 0 0 0 0
1/T (K-1)

Figure 1. An Arrehenius ploy with all the average rate constants for all eight reactions.

The slope can be used to find the activation energy using the following.

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 −Ea
m=
R

−E a
−7463.8=
8.314

Ea =62,054.03 J mol-1

The Eyring equation is used to find both the enthalpy and the entropy of activation.

k k B ∆ S¿ ∆ H¿
ln () ( )
T
=ln
h
+
R
−
RT
(3)

The intercept of the below graph can be used to find entropy of activation, and the slope
can be used to find enthalphy of activation.

ln(kavg/T) vs (1/T)
0

-2
ln (Kavg/T) (1/K)

-4

-6

-8

-10 f(x) = − 7146.25 x + 12.35

R² = 0.97
-12
0 0 0 0 0 0 0 0 0
1/T (K-1)

Figure 2. An Eyring plot with all the average rate constants for all eight reactions.

∆ S¿ kB
y−intercept =b= +ln ⁡( )
R h

∆ S¿ 1.38 x 1 0−23
12.347= + ln ⁡( )
8.314 6.62 x 1 0−34

ΔS*= -94.89 J mol-1 K-1

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 −∆ H ¿
m=
R

−∆ H ¿
−7146.3=
8.314

ΔH*=59,414.34 J mol-1 K-1

Table 3. End values from experiment; activation energy, entropy, and enthalpy of
activation.

Activation Energy (J mol-1) Entropy (J mol-1 K-1) Enthalpy (J mol-1 K-1)

62,054.03 -94.89 59,414.34

Discussion
Flash photolysis can determine the kinetic properties during the isomerization of
4-anilino-4’-nitroazobenzene. The rate constants can be degarded as pretty accurate; they
are as follows: 0.00415 s-1 for 30 °C, 0.0095 s-1 for 40 °C, 0.0147 s-1 for 50 °C, and
0.0424 s-1 for 60 °C. A high R2 value means that the data is follows a tight trendline. All
the samples have a R2 value of over .94 except for 40 °C Trial #1, which means that the
rate constants are accurate.

The trend of the rate constant is hypothesized to increase as temperature

increases. This is because as temperature increases, the reaction will proceed faster. This
is confirmed with expiremental results. Additionally, with literary research, the rate
constants of the experiments can be evaluated. For example, the literary determination of
the 50 °C rate constant is 0.01 s-1, which is a difference of 0.0047, which is a percent
error of 47.00%.2 This is a very significant error, which will be discussed later.

The activation energy was determined to be 62,054.03 J/mol. This has a percent
error of 13.81%, with the true value being 72,000 J/mol. 2 This is a pretty close
measurement, especially considering that the maximum absorbance wavelength of the
literary experiment is 435 nm, exactly like the experiment done. The enthalpy of
activation is 59,414.34 J/Kmol and the entropy of activation is -94.89 J/Kmol. The R 2

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values of both these activations are above 0.97, meaning that data is very precise in the
Arrhenius and Eyring equations. It is right that the entropy of activation is negative – cis-
4-anilino-4’-nitroazobenzene is an unfavorable form, meaning that it does not want to be
in the cis structure. This would force entropy to be negative. The enthalpy is expected to
not be very large, as it is only a change of formation and does not require any type of
bond breakage or something of that sort.

The use of the following equation can give an estimate of the activation energy at
specific temperatures.

Ea =∆ H ¿ + 2 RT (4)

The activation energies at 30 °C and 40 °C are calculated in the supplementary section

and are 64,455.12J/mol and 64,621.40J/mol respectively. There is a very small
difference in the above calculations and the overall activation energy found, with percent
errors of 3.87% and 4.14%, respectively. The same equation can be used to find the
enthalpy of activation, with answers being 57 , 013.25 J/mol and 56,846.97 J/mol
respectively, with calculations in the supplementary section of the report. These numbers
have percent errors of 4.04% and 4.32%, meaning that the equation can give a good
estimate of the enthalpy of activation, alongside the activation energy.

The largest source of error is timely execution of the experiment, especially

revolving around taking the cuvette from the spectrophotometer and flashing it. During
one of the trials at 40 °C and both 60°C trials, the max absorbance wasn’t found at the
time of the flash. This could be due to the fact that there was some human error in
removing the cuvette and making sure to minimize the time the cuvette spent outside of
the spectrophotomer. Additionally, there is other light shining into the cuvette when it is
taken out of the spectrophotometer, mainly just the room lighting. This could cause
variation in the results. The best solution would be to achieve a way to automate the flash
(as spoken about later), to eliminate both the unwanted additional time spent outside the
cuvette and outside light sources.

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Chemical Engineering Question
The most important part of creating a system to take a flash automatically would
be to make sure that no other light would hit the sample after the flash is done. How I
would go about this is to keep the spectrometer almost as is, but right on the top of the
hood, there would be a small flash. There would be a lid on this hood. How it would
work is that the hood would lift after 30 seconds (or whatever time the experiment
required), and then automatically the hood would be lowered to minimize additional
exposure of the sample to any light source. Having an automated process would allow for
even more accurate results. There would be no spare time involved in moving the sample
in and out of the spectrometer. Additionally, when the sample is removed, the is regular
room lighting that hits the sample. Therefore, it is not perfectly just the flash hitting the
sample. If this automated process was designed and created, this would eliminate that
room lighting from compromising the flash photolysis.

References
1. Baker, C.J.; Dowd, S.E.; Gibson, B.; Hisao, G.S.; Lanni, E.J.; McCurry, D.A.;
Rabe, P.C.; Schilter, D.; Schmitt, K.G. Experiment 04. CHEM 315 Laboratory
Notes [Online] 2012. http://compass.illinois.edu (accessed Oct 6, 2019).
2. Hair, Sally R., et al. “An Easily Implemented Flash Photolysis Experiment for the
Physical Chemistry Laboratory: The Isomerization of 4-Anilino-4-
Nitroazobenzene.” Journal of Chemical Education, vol. 67, no. 8, 1990, p. 709.,
doi:10.1021/ed067p709.

Supplementary Material

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 ln(A∞ -A) vs. Time at 30 C Trial #1
0

-1

-2
ln(A∞-A)

-3

-4 f(x) = − 0 x − 3.48
R² = 0.95
-5

-6
0 50 100 150 200 250 300 350
Time (sec)

Figure 3. Plot of ln(Ainf-A) vs time at 30 C for trial #1.

Ln(A∞ -A) vs Time for 30C Trial #2

0
-0.5
-1
-1.5
-2
ln(A∞ -A)

-2.5
-3
-3.5
-4 f(x) = − 0 x − 3.36
R² = 0.96
-4.5
-5
0 50 100 150 200 250 300 350
Time (sec)

Figure 4. Plot of ln(Ainf-A) vs time at 30 C for trial #2.

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 Ln(A∞ -A) vs Time for 40C Trial #1
0
-1
-2
-3
-4
Ln(A∞ -A)

-5 f(x) = − 0.01 x − 3.9

-6 R² = 0.28
-7
-8
-9
-10
0 50 100 150 200 250 300 350
Time (sec)

Figure 5. Plot of ln(Ainf-A) vs time at 40 C for trial #1.

Ln(A∞ -A) vs Time for 40C Trial #2

0
-1
-2
-3
Ln(A∞ -A)

-4
f(x) = − 0.01 x − 3.7
-5 R² = 0.93
-6
-7
-8
0 50 100 150 200 250 300 350
Time (sec)

Figure 6. Plot of ln(Ainf-A) vs time at 40 C for trial #2.

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 Ln(A∞ -A) vs Time for 50C Trial #1
0
-1
-2
-3
Ln(A∞ -A)

-4 f(x) = − 0.01 x − 2.91

-5 R² = 0.98
-6
-7
-8
-9
0 50 100 150 200 250 300 350
Time (sec)

Figure 7. Plot of ln(Ainf-A) vs time at 50 C for trial #1.

Ln(A∞ -A) vs Time for 50C Trial #2

0
-1
-2
-3
Ln(A∞ -A)

f(x) = − 0.02 x − 2.41

-4 R² = 0.98
-5
-6
-7
-8
0 50 100 150 200 250 300 350
Time (Sec)

Figure 8. Plot of ln(Ainf-A) vs time at 50 C for trial #2.

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 Ln(A∞ -A) vs Time for 60C Trial #1
0
-2
-4
f(x) = − 0.02 x − 2.78
-6 R² = 0.56
Ln(A∞ -A)

-8
-10
-12
-14
-16
0 50 100 150 200 250 300 350
Time (sec)

Figure 9. Plot of ln(Ainf-A) vs time at 60 C for trial #1.

Ln(A∞ -A) vs Time for 60C Trial #2

0
-1
-2
-3
-4
Ln(A∞ -A)

-5 f(x) = − 0.02 x − 3.37

R² = 0.51
-6
-7
-8
-9
-10
0 50 100 150 200 250 300 350
Time (sec)

Figure 10. Plot of ln(Ainf-A) vs time at 60 C for trial #2.

Calculation S1.

Ea =∆ H ¿ + 2 RT

Ea =59,414.34+2(8.314 )¿303.15)

Ea =64,455.12 J /mol

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Calculation S2.

Ea =∆ H ¿ + 2 RT

Ea =59,414.34+2(8.314 )¿313.15)

Ea =64 , 621.40 J /mol

Calculation S3.

Ea =∆ H ¿ + 2 RT

62,054.03=∆ H ¿ +2(8.314)¿303.15)

∆ H ¿ =57013.25 J /mol

Calculation S4.

Ea =∆ H ¿ + 2 RT

62,054.03=∆ H ¿ +2(8.314)¿313.15)

∆ H ¿ =56,846.97 J /mol

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