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Name and ID: Stephanie Wang 106013 Quiz Section: AA Lab Partner: Ariel

Experiment 2: Chemical Kinetics

Part I: A Clock Reaction Part II: Crystal Violet-Hydroxide Reaction Note: All sections of this report must be typed.

By signing below, you certify that you have not falsified data, that you have not plagiarized any part of this lab report, and that all calculations and responses other than the reporting of raw data are your own independent work. Failure to sign this declaration will cost you 5 points. Signature:

Grading: 60 pts.

(Lab notebook pages are worth 5 pts - total for report and notebook is 65 pts)

Purpose and Method

Part I: Clock Reaction (3 pts) (purpose, reactions/rate law, method)
We are using this method to dry to find the rate of the reaction using the method of initial rates. To figure this out we keep all of the concentration constant, except one reactant. That reactant's concentration will be varied between runs, and through that we will be able to calculate the rate using the method of initial rates.

Part II: Crystal Violet-Hydroxide Reaction (3 pts) (purpose, reactions/rate law, method)
We are doing this to find the rate using the integrated rate approach. For this we will have to find the CV concentration at different times, and then judge which graph is best. If the plot of CV vs. t is best then it is zero order, if ln[CV] vs t is best then it is first order, so forth. Doing this it will allow us to find the order fo the reaction, then allowing us to find the total rate reaction equation.

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Data, Calculations and Graphs

Stock Solutions Soln. S2O3 I
2-

Conc. 0.0005 0.010 0.040 0.100

Units mol/L mol/L mol/L mol/L D Time sec. 128.5 80 92 42 214 101 93 115 445 143 106 39 416 63 156 Rate M/s 1.3E-07 2.1E-07 1.8E-07 4.0E-07 7.8E-08 1.7E-07 1.8E-07 1.5E-07 3.8E-08 1.2E-07 1.6E-07 4.3E-07 4.0E-08 2.7E-07 1.1E-07

BrO3 HCl

Experiment Run # 1 2** 3 4 5 6** 7 8 9 10** 11 12 13 14* 15* H2 O mL 0.75 0.50 0.25 0.00 0.75 0.50 0.25 0.00 0.75 0.50 0.25 0.00 0.50 0.75 0.75

Test Tube #1 S2O3 m: 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50
2-

Test Tube #2 I
-

Temp.
+

BrO3 mL 0.25 0.50 0.75 1.00 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50

H 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.25 0.50 0.75 1.00 0.50 0.25 0.25

Celsius C 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.25 0.50 0.75 1.00 0.50 0.25 0.25 25 22.9 24.7 26.5 22.2 22.4 22.7 22.8 23 22.8 22.7 22.5 0 22.1 0

mL

mL

* Measurements made with a drop of 1.0 mM Ammonium Molybdate ** Repeated measurements for calculating k and Ea A drop of 1% Starch indicator solution is included in each run.

Type a sample calculation for the "Rate" here: (2 pts) Rate is equal to (-delta S2O3)/(6 * delta T) So first we must figure out how many moles of S2O3 we used, we know that a total of .5mL or .0005 L was used in the experiment and that the S2O3 was .0005M. From this we can find out that .0005 L x .0005M is equal to 2.5E-7 moles. We then have to find the total volume. We know that 2.5 mL was used so then we divide 2.5E-7 moles/ .0025 L =.0001 M Time it took was 214 seconds, so (-.0001)/( 6*214)= 7.8E-8. Rate is always positive, so negative sign was "dropped."

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Reaction Order Determination for I Experiment Run # Run 1 Run 2 Run 3 Run 4 Temp Celsius 25 22.9 24.7 26.5 S2O3
2-

Initial Concentrations (M) I

-

Time BrO3
-

Rate M/sec 25 22.9 24.7 26.5 1.3E-07 2.1E-07 1.8E-07 4.0E-07

H 0.0010 0.0020 0.0030 0.0040

sec

0.0001 0.0001 0.0001 0.0001

0.0200 0.0200 0.0200 0.0200

0.0080 0.0080 0.0080 0.0080

1 pt

Type your calculation for the concentration of BrO3- here: So BrO3 is .040 M, and we have .5 mL. So we do (.5 mL)(.04M)=.02 mmoles .02 mmoles/ 2.5 mL= .008 M

1 pt

HINT BOX
Recall that since BrO3- and H+ where held constant, the rate law takes on the following form: Rate = B[I-]i Therefore, a plot of log(Rate) vs. log(I-) will yield a straight line with a slope equal to i, the order of the reaction with respect to I-.

X-axis log(I-)

Y-axis log(Rate)

-3.0 -2.7 -2.5 -2.4

-6.9 -6.8 -6.7 -6.4

Place your plot relating to the reaction order for I- here (cover this instruction box so that your graph is an appropriate size). -6.3 Refer to the box above -3.5 -3.0 for hints. -2.5 -2.0 -1.5 -1.0 -0.5 0.0 -6.4
Properly label your graph (labels for axes, including units, and a title).

log(Rate) vs log(I)

2 pts

log(Rate) M/sec

Include a trendline and its equation and R2 value on your graph. This is done by right-clicking -6.5 on one of the data points on your graph and choosing "Add Trendline" from the drop down menu. The first tab asks what type of trendline you wish to use, and the Options tab allows you to include the trendline equation and R2 value.

-6.6 -6.7 -6.8 -6.9

y = 0.7143x - 4.8071 R = 0.7653

Series1 Linear (Series1)

log (I) M

-7.0

)Order with respect to I -:

(round to nearest whole number

1 pt

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Reaction Order Determination for BrO3Experiment Run # Run 5 Run 6 Run 7 Run 8 Temp Celsius 22.2 22.4 22.7 22.8 S2O3
2-

Initial Concentrations (M) I

-

Time BrO3
-

Rate M/sec 214 101 93 115 7.8E-08 1.7E-07 1.8E-07 1.5E-07

H 0.0020 0.0020 0.0020 0.0020

sec

0.0001 0.0001 0.0001 0.0001

0.0200 0.0200 0.0200 0.0200

0.0004 0.0080 0.0120 0.0160

2 pts

X-axis log(BrO3 ) -3.4 -3.1 -1.9 -1.8

Y-axis log(Rate) -7.1 -6.8 -6.7 -6.8

Place your plot relating to the reaction order for BrO 3- here (cover this instruction box so that your graph is an appropriate size). -6.7 Properly label your graph (labels for axes, including units, and a title). -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 -6.7 0.0

log(rate) vs. log(BrO3)

2 pts

Include a trendline and its equation and R2 value on your graph. This is done by right-clicking on one of the data points on your graph and choosing "Add Trendline" from the drop down menu. The first tab asks what type of trendline you wish to -6.8 use, and the Options tab allows you to include the trendline equation and R2 value.

log(Rate) M/sec

-6.8 -6.9 -6.9 -7.0 y = 0.1634x - 6.4357 R = 0.5647 -7.0 -7.1 -7.1 log(BrO3) M -7.2 Series1 Linear (Series1)

Order with respect to BrO3-:

(round to the nearest whole number)

1 pt

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Reaction Order Determination for H+

Experiment Run # Run 9 Run 10 Run 11 Run 12 Temp Celsius 23 22.8 22.7 22.5 S2O3
2-

Initial Concentrations (M) I

-

Time BrO3
-

Rate M/sec 445 143 106 39 3.8E-08 1.2E-07 1.6E-07 4.3E-07

H 0.0020 0.0020 0.0020 0.0020

sec

0.0001 0.0001 0.0001 0.0001

0.0100 0.0200 0.0300 0.0400

0.0080 0.0080 0.0080 0.0080

2 pts

X-axis + log(H ) -2.0 -1.7 -1.5 -1.4

Y-axis log(Rate) -7.4 -6.9 -6.8 -6.4

log(Rate) M/sec

Place your plot relating to the reaction order for H+ here (cover this instruction box so that your graph is an appropriate size). -6.2 Properly label your graph (labels for axes, including units, and a title). -2.5 -2.0 -1.5 -1.0 -0.5 0.0 -6.4 Include a trendline and its equation and R2 value on your graph. This is done by right-clicking on one of the data points on y = 1.5x - 4.4 from the drop down menu. The first tab asks what type of trendline you wish to your graph and choosing "Add Trendline" 2 R =you 0.931 use, and the Options tab allows to include the trendline equation and R value. -6.6 -6.8 Series1 -7.0 -7.2 -7.4 log(H+) M -7.6 Linear (Series1)

log(Rate) vs log(H+)

2 pts

Order with respect to H+: 2

(round to the nearest whole number)

1 pt

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Calculation of Rate Constant, k

Experiment Run # Run 2 Run 6 Run 10 . S2O3
2-

Initial Concentrations (M) I

-

Time BrO3
-

Rate M/sec 80 101 143 Average: Std Deviation: Units: 2.1E-07 1.7E-07 1.2E-07

sec

0.0001 0.0001 0.0001

0.0020 0.0020 0.0020

0.0200 0.0200 0.0200

0.0080 0.0080 0.0080

0.26 0.21 0.15 0.21

M^-2 s^-1

Type your calculation of "k" here: Equation to use is Rate=k(BrO3-)^0(I-)^1 (H+)^2 Run 2= (2.1E-7 M/sec)= k(.008 M)(.002M)(.02 M)^2 2.1E-7 M/sec) / (8E-7 M-3)= k k= .27 M^-2 sec^-1

2 pts

Determination of Activation Energy, Ea

Activation Energy: Uncatalyzed Experiment Run # Ave * Run 13 Temp Celsius 22.7 0 S2O320.0001 0.0001 Initial Concentrations (M) I0.0020 0.0020 H+ 0.0200 0.0200 BrO30.0080 0.0080 Time sec 108 416 Rate M/sec 1.7E-07 4.0E-08

1 pt

* Average value from runs # 2,6, & 10.

Type your calculation of Ea here: For this we use the equation ln(K2/K1)= ((-Ea)/R)(1/T2- 1/T1)) We plug in the following numbers K2= .05 (caluclated form Run 13) K1=.21 (calculated from previous) T2=273 K T1= 295.7 R=8.314 J/K*mol equaling 42729.97 Joules 42.7 kJ
Ea of the uncatalyzed reaction: Activation Energy: Catalyzed with Ammonium Molybdate Calculated from catalyzed runs at different temperatures Experiment Run # Run 14 Run 15 Temp Celsius 22.1 0 S2O320.0001 0.0001 Initial Concentrations (M) I0.0020 0.0020 H+ 0.0200 0.0200 BrO30.0080 0.0080 Ea = Time sec 63 156 Rate M/sec 2.7E-07 1.1E-07 Ea = 42.7 kJ

2 pts

2 pts

1 pt

Ea of the catalyzed reaction:

27.2 kJ

2 pts

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Part II: Crystal Violet-Hydroxide Reaction

Concentration of stock solutions
CV
+ -

1.00E-04 0.10

M M

l max, CV

565

nm

OH

Volume of CV+ stock solution needed to make 25 mL of 1.0 x 10-5 M CV+ is

CV
+

Molar Absorptivity Data

Dilution Factor [CV+] (M) Absorbance

2.5

mL

10.0 4.0 2.0 1.0

1.0E-06 2.5E-06 5.0E-06 1.0E-05

2.4E-02 5.3E-02 1.4E-01 4.2E-01

1 pt

HINT BOX: Before you proceed, make sure you understand what you are doing here. Please refer to the "Intro" document in the Prelab section of the Experiment 2 website for a detailed explanation of the approach we are taking for this part of the lab. You will first evaluate the data for the CV+ standards to obtain a value for Molar Absorptivity that you will then use to convert Absorbance data to [CV+] (Remember: A=ebc)

When working with linear relationships, i.e. straight line plots, one can utilize the "slope" and "intercept" functions in Excel. These are a part of a linear regression function, and calculate the slope of the "best fit line" for a given set of data and the point at which the best fit line for the data will cross the y-axis (y-intercept). To use these functions, click on the cell in which you want the result to appear, B337 for the slope and B338 for the y-intercept, and enter the following:

=slope(H305:H308,G305:G308)
=intercept(H305:H308,G305:G308) H305:H308 represent the cells that contain your y-data, and G305:C:308 represent your x-data. This is a short cut to creating an actual plot of the data and generating the trendline equation of y = mx + b.

You will create three plots on page 9, using the data from run 1 below, to determine the order of the reaction with respect to CV+. If the plot of [CV+] vs t is the most linear, the order will be 0. If plotting ln[CV+] vs t is the most linear, then the reaction is first order with respect to CV+. The third plot that you will make is 1/[CV+] vs t. If this last plot is the most linear of the three plots, then the reaction is second order with respect to CV+.
Once you know the order of the reaction in terms of CV+, you will perform the necessary "slope" functions for the other three runs to determine k' for each run. Be sure to replace the "?" in the label at the top of the data column so that it's clear which calculation you are performing. When you get to the section for determining the order of the reaction with respect to OH-, you will also need to use the "intercept" function mentioned above.

Slope and Y-intercept for Absorbance vs. [CV+] slope y-int

44709.5 -4.950E-02 Molar Absorptivity, e

44709.5

M-1cm-1

2 pts

Run Number 1 2 3 4

NaOH (mL) 2 1.5 1 0.5

DI water (mL) 0.5 1 1.5 2

CV+ (mL) 0.5 0.5 0.5 0.5

mLTotal 3 3 3 3

[CV+]0, M 5.00E-06 5.00E-06 5.00E-06 5.00E-06

[NaOH]0, M 0.0667 0.0500 0.0333 0.0167

*Final [CV+] and [NaOH]

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For the data below place your plots to determine the order with respect to [CV+] on the next page and be sure to identify which one you are using to determine the order of the reaction (enter the order in column "I" next to the appropriate plot and update any column/table titles that contain "?"). Run 1 Run 2 2 pts
Time (s) 9 23 35 45 55 65 75 85 95 105 115 120 135 145 155 Absorbance 0.595 0.576 0.524 0.489 0.439 0.398 0.370 0.331 0.305 0.292 0.274 0.257 0.291 0.228 0.210 [CV+]t 1.44E-05 1.40E-05 1.28E-05 1.20E-05 1.09E-05 1.00E-05 9.38E-06 8.51E-06 7.93E-06 7.64E-06 7.24E-06 6.86E-06 7.62E-06 6.21E-06 5.80E-06 Ln[CV+]t -11.147 -11.177 -11.264 -11.327 -11.424 -11.512 -11.577 -11.674 -11.745 -11.782 -11.836 -11.890 -11.785 -11.990 -12.057 1/[CV+]t 6.937E+04 7.148E+04 7.796E+04 8.303E+04 9.152E+04 9.991E+04 1.066E+05 1.175E+05 1.261E+05 1.309E+05 1.382E+05 1.459E+05 1.313E+05 1.611E+05 1.723E+05 Time (s) 8 18 28 38 48 58 68 78 88 98 108 118 128 138 148 158 Absorbance 0.681 0.652 0.609 0.570 0.536 0.505 0.467 0.442 0.422 0.402 0.380 0.364 0.348 0.335 0.318 0.304 [CV+]t 3.08E-04 2.95E-04 2.75E-04 2.58E-04 2.42E-04 2.28E-04 2.11E-04 2.00E-04 1.91E-04 1.82E-04 1.72E-04 1.64E-04 1.57E-04 1.51E-04 1.44E-04 1.37E-04 ln[CV+]t -8.086 -8.130 -8.198 -8.264 -8.326 -8.385 -8.464 -8.519 -8.565 -8.613 -8.670 -8.713 -8.758 -8.796 -8.848 -8.893

Type an example calculation for determining the CV+ concentration from the absorbance data: To determine CV+ we do (Absorbance + intercept)/(slope) Example would be for the first point in run 1 Absorbance was .595 So (.595+.0495)/(44709.50469)= 1.44E-5

ln([CV+]) vs. time slope -0.0064

Psuedo-rate constant ln([CV+]) vs. time k', Run 1 6.40E-03 slope -0.0055

Psuedo-rate constant
k', Run 2 5.50E-03

2 pts

Page 9 of 11

Place your plot of [CV+] vs time here (cover this instruction box so that your graph is an appropriate size). 1.60E-05 Properly label your graph (labels for axes, including units, and a title). y = -6E-08x + 1E-05 1.40E-05 R of = the 0.9442 2 Include 1.20E-05 a trendline and its equation and R value on your graph. This is done by right-clicking on one data points on your graph and choosing "Add Trendline" from the drop down menu. The first tab asks what type of trendline you wish to 1.00E-05 2 use, and the Options tab allows you to include the trendline equation and R value. 8.00E-06 [CV+]t 6.00E-06 Linear ([CV+]t) 4.00E-06 2.00E-06 0.00E+00 0 50 100 150 200
CV+ Time (s)

[CV+]t

2 pts

Place your plot of ln[CV+] vs time here (cover this instruction box so that your graph is an appropriate size). -11.000 Properly label your graph (labels for axes, including units, and a title). 0 50 100 150 200 -11.200 Include a trendline and its equation and R2 value on your graph. This is done by right-clicking on one of the data points on
your graph and choosing "Add Trendline" from the drop down menu. The first tab asks what type of trendline you wish to -11.400 use, and the Options tab allows you to include the trendline equation and R2 value.

Ln[CV+]t

Ln(CV+)

-11.600 -11.800 -12.000 y = -0.0064x - 11.077 R = 0.9663 Time (s)

Ln[CV+]t Linear (Ln[CV+]t)

-12.200

Place your plot of 1/[CV+] vs time here (cover this instruction box so that your graph is an appropriate size). 2.000E+05 Properly label your graph (labels for axes, including units, and a title). y = 702.48x + 55777 R = 0.96 This is done by right-clicking on one of the data points on Include1.500E+05 a trendline and its equation and R2 value on your graph. !/CV+
your graph and choosing "Add Trendline" from the drop down menu. The first tab asks what type of trendline you wish to use, and the Options tab allows you to include the trendline equation and R2 value.

1/[CV+]t

1.000E+05
5.000E+04 0.000E+00 0 50 100 Time(s) 150 200

1/[CV+]t Linear (1/[CV+]t)

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Run 3 Time (s) 11 21 31 41 51 61 71 81 91 101 111 121 131 141 151 161 171 Absorbance 0.604 0.570 0.535 0.491 0.466 0.439 0.413 0.383 0.360 0.341 0.321 0.298 0.284 0.268 0.255 0.238 0.224 [CV+]t 1.46E-05 1.39E-05 1.31E-05 1.21E-05 1.15E-05 1.09E-05 1.03E-05 9.67E-06 9.16E-06 8.73E-06 8.29E-06 7.77E-06 7.46E-06 7.10E-06 6.81E-06 6.43E-06 6.12E-06 ln[CV+]t -11.133 -11.187 -11.245 -11.323 -11.371 -11.424 -11.479 -11.546 -11.601 -11.648 -11.701 -11.765 -11.806 -11.855 -11.897 -11.954 -12.004

Run 4 Time (s) 9 19 29 39 49 59 69 79 89 99 109 119 129 139 149 159 169 179 189 199 Absorbance 0.652 0.642 0.622 0.599 0.585 0.566 0.551 0.539 0.526 0.515 0.499 0.488 0.478 0.466 0.457 0.447 0.440 0.432 0.423 0.415 [CV+]t 1.57E-05 1.55E-05 1.50E-05 1.45E-05 1.42E-05 1.38E-05 1.34E-05 1.32E-05 1.29E-05 1.26E-05 1.23E-05 1.20E-05 1.18E-05 1.15E-05 1.13E-05 1.11E-05 1.09E-05 1.08E-05 1.06E-05 1.04E-05 ln[CV+]t -11.062 -11.077 -11.106 -11.141 -11.163 -11.193 -11.218 -11.238 -11.260 -11.280 -11.309 -11.329 -11.348 -11.371 -11.388 -11.408 -11.422 -11.439 -11.458 -11.475

2 pts

ln([CV+]) vs. time slope -0.0054

k', Run 3

Psuedo-rate constant ln([CV+]) vs. time 5.40E-03 slope -0.0022

Psuedo-rate constant
k', Run 4 2.20E-03

2 pts

Reaction Order Determination for OHHINT BOX

Recall: rate = k[CV+]c[OH-]o = k'[CV+]c, where k'=k[OH-]o therefore, ln(k') = ln(k) + ln([OH-]o) and since ln([OH-]o) = o*ln[OH-] the following equation will yield a straight line: ln(k') = o*ln([OH-]) + ln(k) Comparing to y = mx+b y = ln(k'), x = ln([OH-]), b = ln(k) The slope of the line gives the order of the rxn m=o
and the rate constant is found by taking the anti-log of the y-intercept.

Run #
1 2 3 4

[OH-]
0.0667 0.0500 0.0333 0.0167

k'
6.40E-03 5.50E-03 5.40E-03 2.20E-03

ln[OH-]
-2.7 -3 -3.4 -4.1

ln(k')
-5.1 -5.2 -5.2 -6.1

2 pts ln(k') vs. ln([OH-]) slope 0.7091 y-int -3.060E+00

Order w.r.t. [OH-], o Rate Constant, k Units on k M^-s^-

1 4.690E-02

2 pts

Page 11 of 11

Results and Discussion Part I

1. Based on your data, write out the complete rate law including value and units for the rate constant. (1 pt) Rate= (.21 M^-2 s^-1)[I- M]^1 [H^+ M]^2 [BrO3 M]^0 2. The literature values for the reaction orders are 1 for BrO3- and I- and 2 for H+ Compare the accuracy of your orders to these literature values. (Calculate the % error.) Discuss your most likely sources of error. (2 pts) My calculated values for BrO3 was a reaction order of 0, and my calculated reaction order for H+ was 2. Percent % experimental-theorectical/ theoretical for BrO3: (0-1)/1 so 100% percent error For H+ percent error is 0% Most likely point of error was that the BrO3's values could have been misculated, or the data could have been faulty. It is very likely that we did not get accurate enoguh data to calculate a good rate value.

3. How do the activation energies for the catalyzed and uncatalyzed reaction compare (include a % difference in your discussion)? Is this in line with what is expected? (2 pts) My catalzyed reaction activation energy was 27.2 kJ and my uncatalyzed reaction activation energy was 42.7 kJ. The percent difference between the catalyzed and uncatalyzed was 44.3%. This was what I expected, because

Part II
1. Based on your data, write out the complete rate law including value and units for the rate constant. The literature values of the orders with respect to CV+ are and OH - are 1 and 1 respectively. How do your values compare? (2 pts) Rate M/s= (.-469 1/Ms)(OH- M)(CV+ M) The order for CV was 1 and the order for OH- was 1. My values are right on with the expected values. 2. Discuss your largest source of error in Part II. (2 pts) Our graphing calculater with the absorbance mearsureing data program broke down half way, so we had to work with another group's graphing calculator. This may have presented some confounding variables in our results.

Laboratory Waste Evaluation (1 pt)

Laboratory waste is considered anything generated during an experiment that is disposed of down the sewer drain, thrown in the garbage, collected in a container for disposal by the UW Environmental Health & Safety department, or released into the environment. Based on the written lab procedure and your actions during the lab, list the identity and approximate amount (mass or volume) of waste that you generated while performing this experiment. Total waste: 9mL .0005M Na2S2O3 9mL .010M KI 9mL .040M KBrO3 9mL .100M HCl 9mL H2O 50mL of CV+ total 5mL NaOH .