Rate Law Determination of the Crystal Violet Reaction Purpose: To determine, experimentally, the order of the reaction between

crystal violet and sodium hydroxide with respect to crystal violet, using light absorbtion with a spectrovis To prepare the following three graphs of data, in order to determine the order of the reaction: o [CV+] vs. time o ln [CV+] vs. time o 1/[CV+] vs. time To determine the rate constant, k, for this reaction. To determine the half-life for this reaction.

Background Information: In this experiment, you will observe the reaction between crystal violet and sodium hydroxide. One objective is to study the relationship between concentration of crystal violet and the time elapsed during the reaction. The equation for the reaction is shown here:
N(CH3 )2 N(CH3 ) 2 OH C N(CH3 )2

+ C

N(CH3 )2 + OH

N(CH3 )2

N(CH3 )2

A simplified (and less intimidating!) version of the equation is: CV+ + OH(crystal violet) (hydroxide ion) The rate law for this reaction is in the form: rate =
[CV + ] = k[CV+]m[OH-]n, t

CVOH

where k is the rate constant for the reaction, m is the order with respect to crystal violet (CV+), and n is the order with respect to the hydroxide ion. Since the hydroxide ion concentration at the beginning is1000 times larger than the concentration of crystal violet, [OH-] will not change appreciably during this experiment [OH-] is essentially constant. This enables us to rewrite the rate law as: rate =
[CV + ] = k [CV+]m, where k = k [OH-]n t

Note: k is sometimes referred to as the pseudo rate constant, because [OH-] is also built into it. Since the psuedo rate constant includes [OH-], k does not actually remain constant, like a true rate constant would, as k will vary if [OH-] is varied.

Thus, you will be able to determine the order with respect to crystal violet ( m), but not the order with respect to hydroxide (n), by collecting concentration vs. time data for crystal violet, CV+. As the reaction proceeds, a violet-colored reactant will be slowly changing to a colorless product. Using the green (564.5 nm) light source of a computer-interfaced spectrovis, you will monitor the absorbance of the crystal violet solution with time. We will assume that absorbance is proportional to the concentration of crystal violet (Beers law). Materials: Computer, Spectrovis, your brain, 2 x 10-5M Crystal Violet, .10M NaOH, .20M NaOH, distilled water, cuvette, stirring rod, 5 small sigma bottles, pipetters. Procedure: 1. Obtain and wear goggles. 2. Connect the Spectrovis to the computer. Open the Crystal Violet experiment on the desktop of the computer. The program should be pre-set at a wavelength of 564.5 nm. 3. Prepare a blank by filling a cuvette 3/4 full with deionized water. Then calibrate the Spectrovis by going to Experiment, and then Calibrate. 4. Make sure the data collection mode is set to Time Based, and the sampling rate is set to take four readings a minute for a total of 10 minutes. This should be pre-set into the program. 5. Obtain ~ 20 mL of .1M NaOH, .2M NaOH, and 2 x 10-5M CV solutions into your small sigma bottles. Have a fourth sigma bottle filled with distilled water for rinsing your pipette. Have a fifth sigma bottle in which the reaction will take place. 6. Empty and discard the contents of the cuvette. Measure 10.0-mL each of 2.0 10-5 M CV and 0.20 M NaOH solutions into a small sigma bottle using a pipette and mix thoroughly with a stirring rod. As soon as possible, rinse the cuvette with a couple ~1-mL portions of the mixture, and fill the cuvette full with the mixture. 7. Place the cuvette into the Spectrovis, with a lid, click Collect . Allow the reaction to proceed until the the data collection ends on its own. Discard the beaker and cuvette contents as directed by your instructor. 8. Rinse your pipette containing the .2M NaOH with distilled water. Repeat steps 6 and 7 using 0.10 M NaOH instead of 0.20 M NaOH. Graphs: Create the graphs as discussed above in the purpose, in order to determine whether the reaction is zero, first, or second order. Attach these three graphs to your lab report. Calculations and Conclusions: 1. Determine the pseudo rate constant, k, for each trial, from the slope of the graph for your linear plot (k = slope for zero and first order and k = slope for second order). Be sure to include correct units for the rate constant. Why are these values not the same meaning, shouldnt k be a constant for a reaction at a given temperature?

2. Was the reaction zero, first, or second order, with respect to the concentration of crystal violet? Did the concentration of NaOH have any effect on the reaction order of CV+? Explain your answer using your graphs as appropriate justification. 3. Write a general rate law expression for each graph for the reaction, in terms of crystal violet. (Use the form: rate = k [CV+]m; omit [OH-]). Use numeric values for kand m. 4. What is the half-life of crystal violet in each trial? Calculate this for each trial using an appropriate half-life equation, and the pseudo rate constant. 5. Are the half-lives for each trial the same? Why or why not? 6. From the ratio of the two k values, determine the reaction order with respect to OH- (the value of x). Clearly show your calculations in your lab report. You will need to use the NaOH concentrations after dilution with CV. Note: The value of x should be an integer. If your value is not an integer, it is because of experimental error (probably in measuring and adding the NaOH solutions). If necessary, round your x value to the nearest integer. 7. Calculate the true rate constant (k) value from each of the k values. Be sure to use OHconcentrations that have been adjusted for dilution. Finally, average the two k values obtained. Again, be sure to watch significant figures and use proper units. 8. What happens to the reaction rate as each reaction proceeds? Why? 9. You currently have a linear regression model y = ax+b where y is actually equal to ln A , with A representing the absorbance of the solution. We correlated absorbance to concentration. Using your .1M NaOH graph of ln A vs time, write an equation for your linear regression. Now, determine the absorbance after: a. One minute: b. 100 seconds: 10. Using this same graph, your .1M NaOH graph of ln A vs time, how long will the reaction need to run to generate an absorbance of: a. .25 b. .125 11. Using this same graph, your .1M NaOH graph of ln A vs time, numerically what is the y intercept of this equation and what is its significance?