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Lab 11: Beer's Law and Crystal Violet

Advanced Placement Chemistry


Partners: Aruha Khan & Madeline Phillips
April 7th, 2016

A. Purpose: The purpose of this experiment is to collect absorbance data using a


spectrophotometer for crystal violet to generate a Beers law calibration curve and also to
collect absorbance data as a function of time for the reaction of CV with NaOH to
determine the rate law of the reaction.

B. Abstract: The problem of this lab centered around how to find the complete rate law for
the reaction that took place. The reaction of crystal violet with sodium hydroxide was
experimentally determined to be first order with respect to crystal violet. The pseudo rate
constants of both trials of experiments were found to be k'1 = 1.373E-2s^-1 & k'2 =
1.325E-2s^-1. The rate law of the overall reaction was determined to be Rate = 0.137 [CV]
[OH]. These results were found by performing an experiment that found a calibration curve
for Beer's law as well as two graphs of absorbance v. time.

C. Pre-Lab:
1.
a.) Based on the absorption spectrum of 25 m crystal violet in figure 1 and taking into
account the considerations that follow, what wavelength should you use for the Beers
law calibration curve and subsequent reaction of CV with NaOH? Please explain your
answer. The wavelength used should be about 590nm. This wavelength does not actually
work though, as this would result in over-saturation of light. In general the solution will
be most sensitive at a point right before the peak, or 565nm.
b.) Simulate the instrument readings you will get in Part 1 of the experiment by doing the
following: Trace Figure 1 onto your paper. Draw a vertical line at the wavelength you
have chosen, intersecting the absorbance curve at that wavelength. Where your vertical
line intersects the absorbance curve is the absorbance value your instrument should

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read for the stock 25m crystal violet solution. Keeping in mind Beers law from
Equation 1, and being mindful that the wavelength and path length are fixed, draw Xs
on your vertical line where you expect the absorbance values will be for the diluted
solutions you prepare in Question 2. Use appropriate ratios of concentrations to
determine where on the vertical line to make your marks. Used Beer's law equation (A =
abc): 1.5 (found from graph) = a * 1 (given) * 20m, solving for a. Use for each dilution.

2. A calibration curve requires the preparation of a set of known concentrations of CV, which
are usually prepared by diluting a stock solution whose concentration is known. Describe
how to prepare 10mL of a 5-, 10-, 15-, and 20-m crystal violet using a 25m crystal violet
stock solution. The diluted solutions can be prepared by using distilled or deionized water.
Specifically, use the dilution equation to get her these values. For example, the algebraic
equation to find the amount of distilled water to use in the 20m concentration should be:
(25m) (V1) = (5m) (10mL). So the diluted solutions must use 2, 4, 6, and 8mL for 5, 10,
15, and 20m respectively.
3. During the reaction of CV with NaOH, do you expect the spectrophotometers absorbance
reading to change? How do you expect it to change if such a change is anticipated (increase,
decrease, no change) as the reaction proceeds. Explain your reasoning. The absorbance

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should decrease because as the reaction proceeds, there should be a lower amount of moles
of crystal violetas they are being used to drive the reaction forward. Lower moles in this
case means lower absorbance.
4. Answer the following questions for a reaction of CV with NaOH in these two scenarios: a
solution with a 1:1 NaOH:CV mole ration and a solution similar to what you will be using
with a 1000:1 NaOH:CV ratio.
a.) Using your prior knowledge of reaction stoichiometry, what is the final percentage of
each reactant remaining if each reaction went to completion? Show work and reasoning
to justify your answer. For the one-to-one ratio, the final percent of reactant remaining
should be 0% for each substance, as there are equal amounts, so they are both limiting
reactants. For the one thousand-to-one ration, about 99.9% should be remaining of the
sodium hydroxide, and 0% of the crystal violet should be left, as the CV is the limiting
reactant.
b.) Based on this result, describe how one gets equations 3 and 4 from equation 2 in the
explanation section. Equations 3 & 4 are essentially broken down and simplified
versions of equation 2. These equations are approximations of equation 2, made to
simplify the analysis process.
5. Describe the graphical analysis that can be done to determine the order and the value of the
pseudo-rate constant k*, of a chemical reaction from concentration data collected through
time. To find the rate order from a graph, divide one by the concentrations of the CV ions
and/or take the natural lot of the concentrations of the CV ions. These both indicate either
first or second order reactions, and when plotted, whichever one describes a straight line will
be the actual rate order. Once the rate order is known, the integrated rate law can be used to
find the value of k*.
6. Based on your answer to questions 3-5, design an experiment for the reaction of CV with
NaOH and describe the subsequent data analysis to accomplish the Central Challenge, the
determination of (i) the value of w (the order with respect to CV) and (ii) the pseudo-rate
constant found in the rate law in Equation 3. For simplicity, use 10.mL for the combined

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volume of CV and NaOH because it is a bit more than enough to fill cuvettes appropriately.
Experiment/procedure is listed in the procedure section of this lab report.
7. Answer the following questions after examining figure 3 to address the issue of when to stop
collecting data.
a.) For early parts of the three different reactions in Figure 3, all three curves seem
relatively linear with different slopes. But as the reactions progress through time, at
roughly what concentration level would you say some graphs start to look non-linear?
The lowest concentration level where the nonlinear behavior of the graph is revealed is
at about 3M. This shows that both the second and first order reactions are curved,
meaning the reaction must be zeroth order.
b.) Given that you dont yet know the order of the reaction of CV with NaOH, how might
Figure 3 help you to decide when to stop collecting data? Think in terms of percent
completion instead of concentration. I would not stop collecting data until after 80% of
the crystal violet has been used in the reaction. This would ensure that the curves in the
slopes for whatever orders the reaction isn't are revealed.

D. Procedure:
Part I
1.) Use a cuvette of distilled water to calibrate your spectrophotometer according to its
instructions.
2.) Configure the spectrophotometers wavelength to 565nm.
3.) Prepare 10-mL of the following crystal violet solutions in a 10-mL graduated cylinder: 25m
solution, 20m solution, 15m solution, 10m solution, & 5m solution, separately.
4.) Pour and appropriate amount of each aforementioned solution into a cuvet (clean between
uses with distilled water & handle with ridged sides). Place each cuvet of solution into
spectrophotometer and record absorbance.
Part II
1.) Pour 5-mL of CV and NaOH into two separate 10-mL graduated cylinders.
2.) Start a timer as soon as you combine the crystal violet and sodium hydroxide into a single
graduated cylinder.

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3.) Pour the combination solution prepared in step two into a cuvette and insert the cuvette into
the spectrophotometer.
4.) Record the absorbance of the solution into the spreadsheet every twenty seconds until eight
minutes gave passed, then stop timing and record exact time elapsed.
5.) Repeat steps one through four with a a combination of 6-mL of crystal violet and 4-mL of
sodium hydroxide, as illustrated in steps one and two.
6.) Clean all laboratory equipment and dispose of solutions as instructed.

E. Materials Used:
Berol-type pipet
10-mL graduated cylinder
Sodium hydroxide, NaOH, 9-mL, 0.200M
Crystal violet, CV, 11-mL, 25m
Water, distilled or deionized
Timer
Spectrophotometer
Blank cuvets
MacAir (w/ LoggerPro software)
F. Data:

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G. Calculations/Results:
Statement of Results: The complete rate law for the crystal violet - hydroxide reaction was found
to be Rate = 0.137 [CV] [OH]. This was done by using Beer's law, the dilution equation and an
equation which related k', hydroxide concentration, and k.
Firstly, find the slopes of the natural log graphs of T1 and T2. These values will be equal to k'.
k'1 = 1.373E-2s^-1 & k'2 = 1.325E-2s^-1 of T1 & T2
Secondly, use the dilution equation to find the molarities of the hydroxide in T1 and then in T2.
(0.200M) (5mL) = (M2) (10mL); M2 = 0.10M (T1)
(0.200M) (6mL) = (M2) (10mL); 0.12M (T2)
Thirdly, plug the aforementioned values into this equation: ([OH-]1/[OH-]2)^m = (k')1/(k')2. Solve
for m.
(0.10M)/(0.12M)^m = (1.373E-2s^-1)/(1.325E-2s^-1)
0.83^m = 1.036
m = 1 (approximately)
Fourthly, use the k' and the OH concentration values from T1 in this equation: k = k'/[OH-]^m.
Solve for k.
k = 1.373E-2s^-1/0.10M
k = 0.137M^-1s^-1

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Lastly, write the full rate law.
Rate = 0.137 [CV] [OH-]

H. Analysis: The point of this lab was essentially to determine the full rate law of the
crystal violet - sodium hydroxide reaction. In doing this, the lab taught me how to use a
calibration curve to find the concentration value of crystal violet (with Beer's Law). It also
taught me how to use graphs of the concentrations, or natural log or reciprocal of the
concentrations, to find which rate order the crystal violet was. Then I learned how to find a
k' value for the hydroxide, and from that calculate the actual k value and then the full rate
law. In doing this, the lab succeeded, as I was able to calculate a full rate law for the
reaction. Possible sources of error in the lab include the use of Berol-type pipets and the
remnants of distilled water in the cuvets used. Using Berol-type pipets to measure out
milliliters of hydroxide and crystal violet decreased the precision with which my group was
able to attain our amounts of said chemicals. This means that we quite possibly had more or
less moles of either crystal violet or hydroxide. The possibilities caused by this are quite
numerous, and our rate constant valueeven the order attained for the hydroxidecould
be inaccurate/incorrect as a result of this. Also, the leftover distilled water in the cuvets
would've diluted both the crystal violet - distilled water solutions more than they should've
been, it also (likely) slightly diluted the crystal violet - hydroxide solutions. This would've
decreased the absorbance values that we attained more than they should've been, meaning
our k', and thus our k, could possibly be lower than it should be.

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