Ickes, Reitz, Wilmes 1 Beginning Questions How do the amounts of reactants present at any given time affect the

rate of reaction at that time? What is the order of the reaction and the rate constant at 23.3 C? In this experiment our goal was to find the order of reaction and reaction rate for the following equation: S2O82- + 3I- 2SO4- + I3However, this reaction occurs so quickly that it would be near impossible in our laboratory to collect accurate data. Therefore, we introduce a second reaction, which will aid us in timing the first. This reaction is 2S2O32- + I3- 3I- + S4O62-. By examining the second equation, it can be seen that one of the products of the second reaction (I-) is a reactant in the first equation. This means that we can find the rate of the first reaction (since it is near instantaneous), by timing the rate thiosulfate (S2O32-) is used up in the second reaction and dividing that value by two, since two thiosulfate molecules are used for every iodide molecule. Safety Considerations Do not ingest any of these substances and wear eye protection at all times. Many of these substances are eye, skin, and respiratory irritants, including Na2S2O8, Na2S2O3, KI, KNO3, and K2SO4. KNO3 is toxic to the blood; KI is toxic to the thyroid gland. It is not advisable to come into contact with large quantities of any of these substances. Take particular care with the sodium persulfate (Na2S2O8), as it can be very hazardous to the skin. When transferring it from container to container, minimize splash potential by pouring carefully and cautiously. When combining this substance with another in the experiment, pour the beaker containing the Na2S2O8 into the other beaker, again to minimize splash potential. All trials should be done under the fume hood to minimize inhalation potential of harmful vapors.

Ickes, Reitz, Wilmes 2 Procedures and Tests Materials: 2 150ml beakers Na2S2O3 KNO3 Procedure: 1 250ml beaker Na2S2O8 K2SO4 Stopwatch KI Packing peanuts

Take the two (2) 150ml beakers. Label them Beaker A and Beaker B.

Measure out the appropriate amount of the specific aqueous solutions in each, according to the following table (Table 1). Note that Beaker A will always consist of 10.00 ml sodium thiosulfate (Na2S2O3), two (2) packing peanuts, and varying amounts of potassium iodide (KI) and potassium nitrate (KNO3). Beaker B will always consist of varying amounts each of sodium persulfate (Na2S2O8) and sodium sulfate (K2SO4). Table 1 Beaker A 10.00 mL Na2S2O3 plus Beaker B 2 packing peanuts KI Na2S2O8 K2SO4 KNO3 (mL) (ml) (mL) (mL) 20 0 20 0 20 0 15 5 20 0 10 10 20 0 5 15 15 5 20 0 10 10 20 0 5 15 20 0 10 10 10 10

Trial 1 2 3 4 5 6 7 8

After filling each beaker with the prescribed amounts of solution, pour the contents of beaker A into the 250 ml beaker. Since beaker B has the more harmful substance in it (Na2S2O8), it is desirable to pour this solution into the other, to minimize the splash potential of that substance. Now, prepare to pour the contents of beaker B into the 250ml beaker, with the contents of beaker A in it. Have the stopwatch ready to begin timing. When ready, pour the contents of beaker A into the 250ml beaker while simultaneously starting the stopwatch. Observe the length of time it takes for the solution to turn blue-black. Record this value. After completing the trial, empty the blue-black waste solution in the nonhalogenated waste container. Completely rinse out and dry the 250ml beaker before

Ickes, Reitz, Wilmes 3 beginning the next trial. Proceed through the different combinations of aqueous solutions, according to Table 1, until done. Data, Observations, Calculations, and Graphs Below is the recorded length of time it took for each trial to experience a color change. Also listed is the average value for each trial. Trial Time (s) Avg. (s) 34.29, 37.8, 38.76, 38.6, 1 36.88, 35.0, 40.51, 30.1 36.49 46.87, 47.50, 54.29, 47.1, 2 43.6, 44.5 53.43, 42.6 47.49 69.5, 72.15, 62.5, 65.5, 3 66.63, 74.88, 67.0, 67.67 68.23 132.15, 131.42, 120.6, 4 123.0, 129.3, 113.2, 124.85 58.25, 50.1, 55.7, 54.2, 5 56.2, 54.3 54.79 85.5, 73.5, 85.3, 80.2, 6 81.1, 80.3 80.98 153.5, 156.8, 170.3, 7 149.0, 152.9, 156.2 156.46 130.8, 130.4, 137, 124.1, 8 143.3, 144.6 135.03 The first challenge in answering our beginning questions is finding the order of the reaction. The first step in this is calculating the molarity of each reactant in the solution. For this we used the equation M1V1 = M2V2. A sample calculation is shown for Trial 1. Trial 1, Thiosulfate: (0.01L)(0.010M) = M2(0.050L) M2 = 0.002M Listed are the calculated concentrations. Trial 1 2 3 4 [KI] (M) [Na2S2O8] (M) 0.088 0.072 0.088 0.054 0.088 0.036 0.088 0.018 Trial 5 6 7 8 [KI] [Na2S2O8] (M) 0.066 0.072 0.044 0.072 0.022 0.072 0.044 0.036

Ickes, Reitz, Wilmes 4 The second step in this is calculating the rate for each trial. This is done using the following formula: Raterxn = [X]f [X]i tf - ti Into this equation, we inserted the only concentration that was kept consistent throughout the entire experiment, that of Na2S2O3. After finding the rate for sodium thiosulfate, we must then divide it by two to find the rate for the reaction of persulfate and iodide. We disregard the negative sign. The following example illustrates this mathematical process. Trial 1: 0.0002 M 0.000 M = (5.48*10-5 M/s)/(2) = 2.740*10-5 M/s 36.49s 0.00s

The rates of reaction for each trial are listed here: Trial 1 2 3 4 5 6 7 8 Rate 2.74E-05 2.02E-05 1.47E-05 8.01E-06 1.83E-05 1.23E-05 6.39E-06 7.41E-06

The next step is to solve for the order of the reaction. There are two methods to solve for this. One way is the algebraic method, involving this equation: Raterxn = k[S2O82-]M[I-]N Find the order of each of the reactants can be done by keeping the concentration of one constant while changing the other and measuring the effect it has on the rate of reaction. The equation for that is: Rate1 = k[S2O82-]M[I-]N Rate2 = k[S2O82-]M[I-]N The method we used for discovering the order of the reaction was the graphical method. To do this, we graphed the rate of the reaction compared to the different concentrations of S2O82- and I-. These graphs are shown here.

Ickes, Reitz, Wilmes 5

Rate of Reaction in Relation to [Na2S2O8]

Rate of Reaction (M/s) 3.00E-05 2.50E-05 2.00E-05 1.50E-05 1.00E-05 5.00E-06 0.00E+00 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08

[Na2S2O8] (M) y = 0.0004x + 2E-06

Rate of Reaction in Relation to [KI]

Rate of Reaction (M/s) 2.00E-05 1.50E-05 1.00E-05 5.00E-06 0.00E+00 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07

[KI] (M) y = 0.0003x + 5E-07

Because connecting these points shows a straight line, we can conclude that each of these reactants is first order. Going back, we can then replace both M and N with 1 in the equation, yielding Raterxn = k[S2O82-][I-] In this reaction, adding the powers of the reactants yields the order for the entire reaction, meaning this is a 2nd order reaction. The final step in discovering the full equation was to find the value for k. This was done by substituting each of the values for initial concentration and rate from each trial back into the rate law. This yielded the following values for k.

Ickes, Reitz, Wilmes 6 k-value (1/Ms) 0.0043 0.0044 0.0046 0.005 0.0038 0.0038 0.004 0.0046 0.0043125

Trial 1 2 3 4 5 6 7 8 Average

Theoretically, these should all equal the same values. However, this rarely happens in a laboratory setting. These values are all close enough for a satisfactory average to be taken and used as substitution in the general rate law. This gives us the specific rate law, which is Raterxn = 4.313*10-3 1/Ms[S2O82-][I-] Claims We claim, in answer to our beginning questions, that the reaction in this experiment is a second order reaction, with the rate constant being 4.313*10-3 1/Ms. Evidence and Data Analysis When we were determining the actual initial concentrations, we did not take into account the potassium nitrate and potassium sulfate, because they were used as fillers in this reaction. The purpose of fillers was to keep the volume constant. Keeping the volume constant enabled us to calculate molarity more accurately. Furthermore, they were not consumed in the reaction, so the concentration of these parts wouldn t change. After determining the initial concentrations of each reagent, we found that the initial concentration of thiosulfate did not change. This is to be expected, because thiosulfate is not part of the reaction that we are measuring. It is only part of the secondary reaction that reduces the tri-iodide ion. In this experiment, the reaction we were trying to find the rate for happened almost instantaneously and was impossible to measure in our laboratory. So, what

Ickes, Reitz, Wilmes 7 was actually measured was the time it too for the thiosulfate to run out. When it was no longer present, the sulfate ion was allowed to fully react with the tri-iodide ion, thus giving us the blue-black color. The tri-iodide is used up in the second reaction. The rate of tri-iodide s disappearance in the second reaction is equal to the rate of formation of the tri-iodide ion in the first reaction, as previously stated. Our calculations shown previously shown support our claim for this being a second-order reaction with a rate constant of 4.313*10-3 1/Ms. The piece of evidence that most supports this is the graphs for each S2O82- and I-. When we varied the concentrations of these, the rate of reaction changed in a linear way. Since both the concentrations of the reactants were first-order, we add them together to get second-order for the overall reaction. There were no specific anomalies in this experiment. Our data all lined up in the same way, pointing the same conclusion. Reading, Reflection, and Post-Laboratory Questions This experiment, as with most experiments, could have had sources of error. The most probably source of this in our trials was human error. This experiment requires very specific, accurately measured amounts of the reactants. It is possible that when we were doing this out of the buret we made a small mistake in what we measured. Also, as always, when transferring liquids from container to container there will occur some loss of volume. That could also affect our data. However, we did not make any major mistakes resulting in spillage, which would be majorly detrimental to the accuracy of our results. In this experiment we were timing how long it took for a reaction to occur, which would then turn the solution blue-black. To do this, we had one person run the stopwatch and another person watching the reaction. This could cause a source error because it takes time for the person to see the reaction and then tell the timer to stop. Thus, the time recorded could be slightly inaccurate. Since our results were the averages of all the trials done in our class, they have a direct correlation to the results of our classmates. Looking back at all the values listed, none are extremely far off from one another. The averages we used for calculations are very acceptable for this experiment.

Ickes, Reitz, Wilmes 8 One question we have after performing this experiment is: does the amount of starch present affect the data gathered? This seems to be a valid question. If there is too little starch, it seems like the solution may take a greater amount of time to change color. If there is a greater amount of starch, it might turn blue-black more quickly. An interesting thing we thought about after this lab was how this reaction rate compares to other reactions. Is it a relatively quick or slow reaction? How will a reaction rate affect the usefulness of that reaction in a real-world application? Before this experiment we had to assume that concentration affected the rate of reaction. Our ideas have changed now, because that idea from the book was proven in the lab. We were able to see how increasing the concentration of the reactants increased the disappearance of thiosulfate and ultimately the rate of oxidation of persulfate. The idea of kinetics can be seen in many facets of everyday life. For instance, we can see how temperature can speed up a reaction, but looking at baking. If you turn up the oven, your cookies are going to bake quicker because the reaction was sped up. Also, we can think about acid rain and it s eroding effects on marble statues. If the concentration of acid doubles in the rain, then it will erode marble at a faster rate. This idea is due to the fact that the rate of the reaction is increased when you increase the concentration.