Lab 2 Kinetics

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The key takeaways are to determine the reaction order and rate constant of the reaction between crystal violet and sodium hydroxide, and to calculate the activation energy of the reaction using the Arrhenius equation.

The objective is to use UV-Vis spectrophotometry to monitor the rate of reaction between crystal violet and hydroxide ion over time, determine the order of the reaction with respect to crystal violet, and calculate the rate constant and activation energy.

The steps to determine the reaction order are to write the general rate law, use a large excess of one reactant so it can be treated as a constant, rewrite the rate law as a 'pseudo' rate law, plot the data in different forms corresponding to different orders, and determine the order based on the best linear correlation.

CHM2046 Lab 2 – Kinetics

DETERMINATION OF RATE LAW AND ACTIVATION ENERGY


BY UV-VIS SPECTROPHOTOMETRY
LAB 2 OUTLINE

OBJECTIVE
The objective of this experiment is to use UV-Vis spectrophotometry to monitor the
rate, as change in a reactant’s concentration over time, of a reaction between the
hydroxide ion (OH–) and crystal violet (C25H30ClN3, or CV), a violet dye that is used as a
biological stain:
C25H30ClN3(aq) + NaOH(aq) → C25H30OHN3(aq) + NaCl(aq)
The order of the reaction with respect to crystal violet, the rate law and rate constant
(k) will be determined.
In addition, activation energy for the reaction will be calculated from the Arrhenius
equation which relates rate constant of a reaction to a specific temperature.

LEARNING OUTCOMES
After this experiment, students will be able to:
1. Understand that reactant concentration affects reaction rate
2. Determine the reaction order with respect to one of the reactants
3. Write the rate law of a reaction
4. Calculate the room temperature rate constant for the reaction
5. Calculate the activation energy for the reaction

SAFETY
Crystal violet solutions may leave lasting stains and cause skin and eye irritation.
Sodium hydroxide solutions are caustic and will cause skin burns. Any skin contact
with either chemical should be washed off immediately. Safety goggles must be worn
at all times in the lab. Before you leave the lab, wash your hands with soap and water.

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CHM2046 Lab 2 – Kinetics

BACKGROUND THEORY
Chemistry:
In pH neutral solutions, crystal violet, also known as triarylmethane, has “conjugation” i.e. a chain of
interchanging double and single bonds, which is associated with color. In alkaline (high pH)
solutions, nucleophilic (electron-rich) hydroxyl ions attack the electrophilic (electron-deficient)
central carbon, thereby interrupting conjugation and producing the colorless triarylmethanol.

+ NaOH  + NaCl

Crystal violet strongly absorbs the yellow light (max = 590nm) of the visible light which, according to
the wheel of complimentary colors below, is a compliment of violet. The UV-visible absorption
spectrum of crystal violet also shows that the purple wavelengths are not absorbed.

Since NaOH(aq) and the products, triarylmethanol and NaCl(aq), in the mixture do not absorb visible
light, the color of the solution is due only to crystal violet. Therefore, as crystal violet molecules
combine with OH– ions and their concentration diminishes, the violet color of the solution will fade
away until the solution is colorless. In order to record these changes, we use a UV-visible
spectrophotometer which detects color changes better than the human eye, and produces
quantitative data.

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CHM2046 Lab 2 – Kinetics

Determining order of the reaction:


For the crystal violet (C25H30ClN3) / hydroxide ion (OH–) reaction:
C25H30ClN3(aq) + OH– (aq) → C25H31ON3(aq) + Cl– (aq)
The rate law can generally be written as:
rate = k[C25H30ClN3]m[OH–]n (1)
where k is the rate constant, m is the reaction order with respect to C25H30ClN3, and n is the reaction
order with respect to OH–.
In this experiment, we will use a very large excess of OH– ion concentration relative to that of crystal
violet so that only crystal violet will slow down the reaction (i.e. crystal violet will serve a similar role
to that of a limiting reactant). While change in CV over time i.e. [C25H30ClN3]t – [C25H30ClN3]o will be
significant, change in [OH–] will be negligible. Therefore [OH–]n in the rate law (Eqn. 1) can be
treated as a constant, leading to a new “pseudo” rate constant, k’. We can now rewrite the rate law,
called “pseudo” rate law, as:
rate = k’[C25H30ClN3]m (2)
Note that Eqn 1 and Eqn 2 can be manipulated to give true constant, k as:
k = k’/[OH–] (3)
Now, in order to find out if the reaction is 1st order (i.e. m = 1) or 2nd order (i.e. m = 2), we can use
the integrated versions of 1st order and 2nd order rate laws since they have a linear, y = mx + b, form.

Order with
respect to
crystal Integrated rate law Graph Slope Units of k’
violet,
C25H30ClN3
0 [C25H30ClN3]t = –k′t + [C25H30ClN3]o [C25H30ClN3] vs t – k′ M.s–1

ln[C25H30ClN3]t = –k′t +
1 ln[C25H30ClN3] vs t – k′ s–1
ln[C25H30ClN3]o

1 k′ M–1.s–1
2 1/[C25H30ClN3]t = k′t + /[ C25H30ClN3] vs t
1/[C25H30ClN3]o

In view of this, we take a series of absorbance measurements of the reaction mixture at different
times from the moment the reaction starts until it has slowed down or reached equilibrium i.e.
where concentration of the product no longer increases. Notice that in order to use [C25H30ClN3] we

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CHM2046 Lab 2 – Kinetics

would need a Beer’s law “calibration” graph. Since [C25H30ClN3] varies directly with Absorbance, we
simply plot its Absorbance vs Time: (Absorbance) vs Time, OR ln (Absorbance) vs Time, OR
[1/(Absorbance)] vs Time to check for the order. The graph that gives a straight line for your data
determines the reaction order as indicated in the Table above.
The absolute value of the slope of the linear plot equals the pseudo rate constant, k’. Note that,
although the slope may be negative, k’ is always positive. If we know the actual [OH–] we used, we
can use Eqn 1 to find the true rate constant, k, assuming that n = 1.
Determination of the Activation Energy of the Reaction:
The value of the rate constant, k, is constant only at a single (specific) temperature. The different
values of k at different temperatures are related by the Arrhenius equation:
k = A e–Ea/RT (4)
where T (in Kelvin) is temperature; R is the universal gas constant, 8.3145 J.mol−1K−1; Ea (in J·mol−1) is
the activation energy of the reaction; and A is a proportionality constant called the Arrhenius pre-
factor (Note: In this equation, A is not absorbance!). Taking the natural logarithm of both sides of
the Arrhenius equation we get:
ln k = ln A + (–Ea/RT)
which can be rearranged into a more obvious linear, y = mx + b form:
ln k = – (Ea/R)(1/T) + ln A (5)
For a more accurate evaluation of the activation energy, Ea, we will collect data for k1 and k2 at two
temperatures, T1 (25oC i.e. 298K ) and T2 (< 10oC i.e. < 283K). Then Ea is obtained by substituting
k1 and T1 and again with k2 and T2. Subtracting the resulting equations, one from the other, we get a
modified version of the integrated Arrhenius equation:
ln (k2/k1) = – (Ea/R) (1/T2 – 1/T1) (note: ln A – ln A = 0) (6)

Therefore, you will perform the crystal violet (C25H30ClN3) / hydroxide ion (OH–) reaction at room
temperature (25oC) and at a temperature below 10oC (< 10oC). We will adjust [OH–] for dilution and
evaluate the two true rate constants, k1 and k2, respectively, and then use the modified form of the
integrated Arrhenius equation (Eqn 6) to determine the activation energy, Ea, of the reaction.

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CHM2046 Lab 2 – Kinetics

EXPERIMENTAL PROCEDURES
Lab 2 simplified instructions

1. Get cuvette and temperature probe from stock room.


2. Plug in temperature probe and spectrometer (make sure both are displayed, if you are not on the
probe page click the symbol in the top left that looks like a speedometer).
3. Tap the gray box in the upper right and set the sensors to time based, 30 s/sample, 360 s total time.
4. Calibrate the spectrometer. Tap the spectrometer sensor on the probe page and select calibrate,
follow the prompts. It should be a big red box that says ABS. Remember the blank sample is a cuvette
filled with DI water. Align the cuvette so the clear side is matched to the white triangle.
5. Set the wavelength to 590 nm (tap the sensor and hit select wavelength).
6. Take 4.5 ml of the purple solution and put it into a small beaker.
7. The next steps should be carried out with a fast pace. When you are ready for the reaction, add 0.5
ml of the NaOH solution and shake to mix.
8. Quickly measure the temperature of the solution (dip the probe into it, record, and then remove) and
look at the color.
9. Pour the mixture into the cuvette, put the cuvette into the sensor, then hit the play button. Make
sure the clear side is aligned with the white triangle so the laser goes through properly.
10. Measure the temperature and look at the color again when it has finished (6 minutes elapsed).
11. Record your data.
12. Repeat steps 6-11 with the cold purple solution and the cold NaOH (they are in the blue cooler).
13. Clean up and depart.

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CHM2046 Lab 2 – Kinetics

DETERMINATION OF RATE LAW AND ACTIVATION ENERGY


BY UV-VIS SPECTROPHOTOMETRY
CHM2046 LAB 2 REPORT

Name: _______________________________________
SFID: _______________________________________
Date: _______________________________________

Your Grade:

/20
TABLES OF RESULTS:
Kinetics Run I: 1.25x10-5 M Crystal violet vs 0.10 M NaOH at room temperature, T1 =___________ oC
Complete the data table:
Absorbance @ ._ 1 . Color compared to
Time (in sec) Ln (Absorbance)
max = 590 nm (Absorbance) that of test solution
0
30 /////////////////
60 /////////////////
90 /////////////////
120 /////////////////
150 /////////////////
180 /////////////////
210 /////////////////
240 /////////////////
270 /////////////////
300 /////////////////
330 /////////////////
360
1800 = 30min ///////////////// ///////////////// ///////////////// clear

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CHM2046 Lab 2 – Kinetics

Kinetics Run II: 1.25x10-5 M Crystal violet vs 0.10 M NaOH at cold temperature, T2 = _________ oC
Complete the data table:
Changes Observed
Absorbance @ . 1 .
Time (sec) Ln (Absorbance) with your naked
max = 590 nm (Absorbance)
eye
0
30 /////////////////
60 /////////////////
90 /////////////////
120 /////////////////
150 /////////////////
180 /////////////////
210 /////////////////
240 /////////////////
270 /////////////////
300 /////////////////
330 /////////////////
360
1800 = 30min ///////////////// ///////////////// ///////////////// clear

Since we did not measure concentration of crystal violet in this experiment, but its absorbance, and
we know that absorbance is directly proportional to concentration, we can use the plot of
Absorbace vs Time, ln(Absorbance) vs Time, OR [1/(absorbance)] vs Time to determine whether the
order of the reaction is 0, 1 or 2 respectively, at a given temperature. Remember that the graph with
a linear correlation (r2 -value closest to 1) determines the reaction order. Time is on the x-axis for all
graphs.

Transfer your Run I kinetic data as well as that of Run II to MS Excel (or similar) spreadsheet and plot
the graphs for the 0th, 1st and 2nd order reactions as discussed above. Label each graph and display
equation of the line including linear correlation (r2 -value). (6 graphs total). Make sure you have a
title, axis labels and units on the labels. The r2 is the value we care about.

Attach all your graphs to this report.

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CHM2046 Lab 2 – Kinetics

PERTINENT CALCULATIONS
Remember: rate = k[C25H30ClN3]m[OH–]n where n = 0 since excess OH– was used.

1. Refer to your graphs and complete table below:


Linear correlation (r2 – value)
Graph Kinetic Run I Kinetic Run II Average r2 - value
absorbance vs time

ln (absorbance) vs time

1/
(absorbance) vs time

2. Based on the average linear correlation (r2 -value) the reaction order, m, with respect to crystal violet,

CV, is ___________.

3. Write the full rate law: _______________________________

4. The slope, and therefore “pseudo” rate constant, k1’, is __________________ at T1, __________ oC; and

k2’ is __________________ at T2, __________ oC; Use only the graphs of the order you just chose above.

5. Since, for Kinetic Run I, you mixed 1.00 mL of 0.10M NaOH and 9.00 mL of crystal violet solution,
use the dilution equation(C1V1=C2V2; solve for C2) to calculate the initial molarity of NaOH i.e.
once it was in solution but at t = 0 (or before reaction started). Kinetic run II will have the same
value.
Kinetic Run I Kinetic Run II

[NaOH]0: M M

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CHM2046 Lab 2 – Kinetics

6. Use the equation provided, to calculate the true rate constant, k,at each temperature. Use your
values from question 4 and 5:
Kinetic Run I Kinetic Run II
k = k1’/[OH–] k = k2’/[OH–] (Eqn 3)

True rate: k1 = k2 = .

Evaluation of Activation Energy, Ea:


7. Substitute k1, k2, T1 and T2 (remember temperature must be in Kelvin) in the modified form of
the integrated Arrhenius equation we derived on page 4 (Eqn 6) to calculate the activation
energy, Ea, of the reaction, where R = 8.3145 J mol−1 K−1 (Solve for Ea, then substitute values):

𝑘 𝐸𝑎 1 1
ln ( 1 ) = − ( − ) (Eqn 6)
𝑘2 𝑅 𝑇2 𝑇1

The Activation Energy, Ea, = _____ J

--o0o-- END OF LAB REPORT

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