Lab 2 Kinetics
Lab 2 Kinetics
Lab 2 Kinetics
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
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
5
CHM2046 Lab 2 – Kinetics
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.
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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.
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 ___________.
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 = .
𝑘 𝐸𝑎 1 1
ln ( 1 ) = − ( − ) (Eqn 6)
𝑘2 𝑅 𝑇2 𝑇1