E3: Kinetics of The Hydrogen Peroxide/Iodide Reaction

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E3: Kinetics of the Hydrogen Peroxide/Iodide Reaction

Introduction
This is a kinetic study of the reaction that many of you will fondly remember as your General Chemistry Laboratory I Final Practical (Fall 2002). 3 I- + H2O2 + 2 H+ I3- + 2 H2O In this experiment, you will determine the order of the reaction with respect to hydrogen peroxide. You will also have the opportunity to measure the activation energy of the reaction. To accomplish these objectives, the method of initial rates will be used. What this means is that the rate of the reaction will be determined over a short time interval at the very beginning of the reaction; this is when the concentration of products is small, and the complication of the reverse reaction is negligible. Because the time interval of the measurement is small, the average rate over that time interval may be taken as the instantaneous initial rate. The reaction will be carried out in the presence of thiosulfate ion, a reducing agent that is fairly inert toward hydrogen peroxide, but which reduces triiodide ion rapidly: I3- + 2 S2O32- 3 I- + S4O62Further, the reaction will be carried out in the presence of starch, which, as you experienced last semester, turns intensely blue in the presence of triiodide ion. The sudden appearance of a blue color will signal the end of the initial reaction (or measurement) period. The measurement scheme will proceed along these lines: 1. Reaction starts at t = 0; peroxide oxidizes iodide to triiodide which immediately is reduced back to iodide by thiosulfate ion; starch does not turn blue because triiodide has only a fleeting existence. 2. Thiosulfate is consumed as the reaction proceeds; when it is all used up triiodide ion starts to accumulate and the blue color appears suddenly; the time is noted. 3. The amount of thiosulfate consumed can be determined: it went from its original concentration to zero. Most significantly, the change in concentration of thiosulfate is directly related to the change in the concentration of hydrogen peroxide . It will be up to you to examine the stoichiometry of the two reactions and to establish this relationship. 4. Once the change in concentration of peroxide is known, and the time interval over which this change occurred has been measured, the initial rate of the reaction is known.

Prelab Assignment
1. From the data below, calculate the rate law expression for the reaction of A with B. Experiment 1 2 3 [A] 0.050 M 0.100 M 0.100 M [B] 0.050 M 0.050 M 0.025 M Time, s 60 30 120

Describe how you would prepare 500 mL of a solution containing 0.025 M sodium acetate and 0.001% w/v starch. Assume that you have standard reagents and labware available, including solid CH3CO2Na3H2O, a 0.5% w/v stock solution of starch, and a 500 mL volumetric flask. 3. One of your experimental runs contains 40 mL iodide solution, 10 mL thiosulfate solution, 25 mL 1.00 M hydrogen peroxide, and 5 mL water. What is the initial concentration of hydrogen peroxide in this run?
2.

Experimental Procedure
Safety Note Be aware of the toxic/corrosive/flammable properties of the chemicals that may be used or generated in this experiment. Report all chemical spills to the instructor promptly so that clean up can be supervised. If a solution drips down the side of a bottle, please rinse it off carefully. Preparation of Solutions The quantities specified here are sufficient for two groups of two students each doing duplicate determinations. Iodide Solution Supplies: Potassium iodide, sodium acetate, 6 M acetic acid, 0.5% w/v starch solution, 1 L volumetric flask, pipets Prepare 2 L of a solution containing 0.0435 M potassium iodide, 0.0720 M acetic acid, 0.0720 M sodium acetate, and 0.0075% w/v starch. Store in a bottle at room temperature. Thiosulfate Solution Supplies: sodium thiosulfate, 500 mL volumetric flask Prepare 500 mL of 0.025 M sodium thiosulfate. Store in a bottle at room temperature. Hydrogen Peroxide Solution Supplies: 30% w/w hydrogen peroxide solution (density = 1.11 g/mL), 1 L volumetric flask Prepare 1 L of 1.00 M hydrogen peroxide. (Calculation hint: Start by determining the molarity of the 30% w/w solution.) Store in a dark (amber) bottle at room temperature. Determination of Reaction Order 1. Do runs 1, 2, and 3 in duplicate at room temperature. The table below shows what quantity of each solution to use for each run. The procedure for mixing the solutions is described in step 2. 2. Mix the iodide and thiosulfate solutions in a 250 mL Erlenmeyer flask. Dilute the peroxide with the amount of distilled water indicated. Measure the temperature of each solution. Swirl the flask while adding the diluted peroxide solution and note the time of mixing to the nearest second. 3. Record to the nearest second the instant the blue color appears. Measure the temperature. 4. Do each run in duplicate. Iodide 40 40 Solution Volumes (mL) Thiosulfate Peroxide 10 10 10 20 Distilled Water 20 10

Run 1 Run 2

Run 3

40

10

30

Determination of the Activation Energy The reaction must now be run at several different temperatures to determine the activation energy. You already have data for room temperature (approximately 20-22 C). Use the table below to guide you in making a convenient formulation for running this reaction at the temperature of an ice-water bath, and at temperatures slightly elevated from room temperature. Choose conditions so that the reaction is neither too fast nor too slow. Iodide 0 C 30 C 40 C 1. The measurement is the same as that described the Determination of Reaction Order section. An important precaution is that the solutions must be in thermal equilibrium with the bath (whether low or high temperature) before proceeding. 2. Do duplicate runs at each temperature. At the end of the experiment: All solutions may be flushed down the drain with copious amounts of running water. Solution Volumes (mL) Thiosulfate Peroxide Distilled Water

Assignment
All of the following calculations are to be submitted in writing as a coherent whole. This includes all spreadsheet calculations, graphs, and the answers to the questions. Integrate text and spreadsheet materials, and organize your results in the order prompted for the calculations. All the spreadsheets and graphs should be stored on a 3 inch diskette and submitted with your report. Determination of the Reaction Order 1. For each run determine the initial hydrogen peroxide concentration. You must take into account dilution effects. 2. Determine the initial thiosulfate concentration and the change in the thiosulfate concentration. Remember that the initial concentration must take into account dilution effects. 3. From the change in the thiosulfate concentration, calculate the change in the hydrogen peroxide concentration during the time interval measured. 4. Find the average rate of change of the hydrogen peroxide concentration over the time of measurement. This is the average of the reaction. 5. Now find the order of the reaction with respect to hydrogen peroxide as follows. The rate law may be written as follows: r = k[H2O2]n where r is the reaction rate, k is the rate constant, and n is the order of the reaction with respect to hydrogen peroxide. Taking the natural logarithm of this equation gives lnr = lnk + n ln[H2O2]

Make an appropriate Excel plot to find the reaction order and the rate constant at room temperature.

Determination of the Activation Energy 1. Use the data from the high and low temperature runs to calculate the rate of the reaction under these conditions. 2. Given the reaction order already established, and the hydrogen peroxide concentration for this run, find the value of the rate constant at each temperature. Note that your room temperature studies yielded a value of the rate constant at room temperature. 3. Now determine the activation energy of this reaction. The Arrhenius equation may be expressed as: k = Ae-Ea/RT where k is the rate constant, A is the frequency factor, Ea is the activation energy, R is the ideal gas constant, and T is temperature. Taking the natural logarithm of this equation gives lnk = lnA (Ea/RT) Using this form of the Arrhenius equation as a guide, make an appropriate Excel plot of the data to find the activation energy of this reaction.

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