Chemistry 102L Manual - Page 55

Reaction Rate, Rate Law, and Activation Energy

Introduction
A principle goal in chemistry is the prediction and control of chemical reactions. The issue of reaction rate is especially important. Chemists want particular reactions to happen when they want them to and at rates that fit a particular need. An example is the reaction between fuel and air within an internal combustion engine. We want the reaction between mixed fuel and air to occur at a particular moment and at a moderate rate. If the reaction is too fast, the engine will knock; if it is too slow, the engine could backfire. One key way we learn to control a reaction is to observe how its rate is affected by reaction conditions such as the reactant concentrations and reaction temperature. At the end of such a study, the rate of that reaction could be predicted for any set of reaction conditions through a rate law, rate constant, and activation energy. The Rate Law The rate law is a mathematical expression that predicts the rate of a reaction from the concentrations of reactants. This rate law is the product of the rate constant (k) and each reactant concentration taken to some power (almost always 0, 1, 2, -1 or 0.5) (See the example below). The values for the rate constant and the concentration powers have to be measured experimentally. An example of a rate law and its rate constant is shown below. Consider the hypothetical reaction: X + 2 Y > Z Rate is the change of a reactant or product concentration per unit time during reaction (in units of M/sec). Mathematically: Rate = -[X]/t = -[Y]/2t = [Z]/t Example: Suppose the rate law was the following Rate = k [X][Y]2 The rate is first order with respect to [X] which means that it is proportional to [X] taken to the first power ([X]1 ). When [X] is doubled, the rate is doubled. [2]1 = 2 When [X] is tripled, the rate is tripled. [3]1 = 3

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The rate is second order with respect to [Y] which means that it is proportional to [Y] taken to the second power ([Y]2 ). When [Y] is doubled, the rate is quadrupled. [2]2 = 4 When [Y] is tripled, the rate is increased by 9. [3]2 = 9 Careful: the reaction order is not necessarily equal to its coefficient in the overall equation. It could be (as is the case in this example), but it will not always be so. The reaction order must be measured experimentally. k = the rate constant This is calculated from one of the experiments after we determined the powers of [X] and[Y]. To calculate k: choose any experiment plug in the concentrations [X] and [Y] and then the corresponding rate into the rate law. algebraically solve for k.

In addition to controlling the rate of a reaction through the concentrations of its reactants, its rate can also be changed through its temperature. Within a reaction, there is often a particular step in the overall process that slows the entire reaction down. This is often a difficult step where the molecules involved must collide with a minimum amount of energy for the reaction to occur. This minimum energy requirement is called the activation energy. Knowing this energy both helps us predict the reaction rate at other temperatures (and to predict what could be happening in the slow reaction step). The activation energy manifests itself through the rate constant: k = Ae Ea /RT k = the rate constant in the rate law A = a constant for the reaction at all temperatures and concentrations. Ea = the activation energy R = the universal gas constant T = the temperature of the reaction in Kelvin.

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Experimentally, we need an easy way of measuring Ea for a reaction. We need to focus on the effect of Ea on the rate constant (and the resulting rate). Since E a is mathematically tied to T (reaction temperature) within the equation for the rate constant, k = Ae E a /RT , we need to: Hold the reactant concentrations constant such that all the rate changes are due to changes within k. If we do this for the example reaction above, we can group A and the concentrations together as one big constant (bracketed together with the {} below). Rate = {A[X][Y] 2 }e E a /RT Measure how the reaction rate responds as the temperature is changed (T). Plot the natural log of the Rate, ln(Rate), versus the inverse of the temperature (1/T). The slope of this line times the gas constant (R = 8.315 J/molK) is the energy of activation (Ea). The reason this works is outlined below. If we take the natural logarithm of both sides of the rate equation for the example reaction, we will get the following. (We are doing this since the logarithm will eventually free -Ea/RT from the exponent e E a /RT .) ln (Rate) = ln { A[X][Y]2 }e Ea /RT

The logarithm of a product is the same of the sum of the individual logarithms: ln(AB) = ln(A) + ln(B) So, this allows us to separate the constant part of the rate equation (A[X][Y]2 ) and the variable part (e E a /RT ) into separate logarithms: ln (Rate) = ln( A[X][Y]2 ) + ln( e E a /RT ) The natural logarithm (ln) now frees the -Ea/RT from the exponent e E a /RT ln (Rate) = ln( A[X][Y]2 ) Ea /RT Now, this equation looks a lot like the equation for a line. If ln(Rate) is y (the vertical coordinate on the graph) and (1/T) is x (the horizontal coordinate on the graph), the constant ln(A[X][Y]2 ) would be the intercept of the line and -Ea/R would be its slope. y = Intercept + (slope)x Where: y = ln(Rate) x = 1/T Intercept = ln(A[X][Y]2 ) Slope = Ea/R

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After we have measured E a, we can now predict reaction rates at any temperature as well as at any set of concentrations. A third way of controlling a reaction is the addition of a catalyst. Catalysts change the individual steps followed in a reaction and essentially avoid those that slowed the entire reaction down. These catalysts incorporate themselves into the rate law and accelerate the reaction. We will see an example of this in this experiment.

Experimental Objective.
This experiment will give you the chance to observe how the rate of the reaction below is changed by variations in reactant concentrations, temperatures, and catalysts. You will then use this data to determine its rate law, its rate constant, and its activation energy. 2 I- + S2 O8 2- > I2 + 2 SO4 2Experimental Strategy: This reaction is easily measured through the formation of I2 . One creative way of measuring the rate of this reaction is to couple it with a much faster reaction that consumes I 2 . I2 + 2 S2 O3 2- > 2 I- + S4 O6 2This second reaction immediately consumes the I2 generated in the first reaction until the S2 O3 2is used up. As long as S2 O3 2- remains, we can combine the S2 O8 2- reaction and the S2 O3 2- reaction as shown below. Through this reaction, we can easily calculate the amount of S2 O8 2- that remains when S2 O3 2- is used up. (Remember that for every mole of S2 O3 2- used up, half a mole of S2 O8 2- is consumed by the reaction. This is demonstrated below for the starting concentrations: [S2 O8 2-] = 0.100M and [S 2 O3 2-] = 0.005M. At the end of the reaction, the concentration of S2 O8 2is 0.0975M. The concentration of S2 O8 2- changed by (0.100M) - (0.0975M) = 0.0025M from beginning to end of this reaction. Example: In the presence of 0.10 M S2 O8 2- and 0.005 M S2 O3 2-: S2 O8 2- + 2 I> 2 SO4 2- + I2 2 S2 O3 2- + I2 > S4 O6 2+ 2 I S2 O8 2- + 2 S2 O3 2- > 2 SO4 2- + S4 O6 20.100 0.005 0.000 0.000 -(1/2)(0.005) -0.005 +0.005 +(1/2)(0.005) 0.0975 0.000 0.005 0.0025

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When the S2 O3 2- is consumed, I2 builds up and reacts with starch to form a dark blue color. S2 O8 2+ 2 I> 2 S4 O6 2- + I2 (I2 then reacts with starch to form greenish-blue color.)

When the S2 O3 2- is used up, I2 begins to build up from the first reaction. If starch is present, it reacts with the accumulating I2 to form a greenish-blue color. At the instant this color appears, you know all the S 2 O3 2- had been consumed and can easily calculate the amount of S2 O8 2- remaining (as we have already seen). The difference between the initial and final concentrations of S2 O8 2- divided by the amount of time needed for this change to occur is the rate of the reaction. Calculating the rate of the first reaction (the information we want to know):
2 [S2 O8 ] Rate1 = t

Rate1 = Rate of the first reaction [S2 O8 2-] = [S2 O8 2-]final - [S2 O8 2-]initial [S2 O8 2-]initial = the initial (beginning) concentration of S2 O8 2-. [S2 O8 2-]final = the final concentration of S2 O8 2- calculated from its reaction of S2 O3 2-. t = the time that passed during this reaction. As we saw above, for every mole of S2 O3 2- used up, half a mole of S 2 O8 2- was also consumed. If we know the starting concentration of S2 O3 2- and remember it is all used up when the color of the reaction changes, then we can say that half that amount of S 2 O8 2- was also consumed in the reaction. That means that the change in S 2 O8 2- concentration is equal to half the starting (initial) concentration of S2 O3 2-. [S2 O8 2-] = [S2 O3 2-]initial/2 We also know that the time of the color change (tcolor) is also the time that passed during the reaction (t). t = tcolor Now, the rate of the first reaction can be rewritten from information that we either know or can easily measure: Rate1 =
2 [S2 O3 ]0 2t color

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Experimental Objective
In this experiment, you will use these principles to measure the rate of the first reaction for different concentrations and temperatures and apply this data to determine the rate law, rate constant, and activation energy for the oxidation of I- by S2 O8 2-.

Important Notes
This is a two session experiment. Since the solutions you prepare in the first session will also be needed in the second, save your solutions by tightly covering their flasks with rubber stoppers. You may work in groups of 2 (but no more without explicit permission from your instructor). The report form at the end of the procedure must be completed and returned to your instructor one week after completing the experiment. You are also expected to record all results in your notebook as you collect them. Your instructor will be spot checking your work.

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Experimental Procedure:
For clarity, each line in this procedure (and every procedure that follows in this manual) is preceded with a symbol that represents what you need to do in that step. The symbol means that you have to carry out a task. The () symbol means that you need to make an observation. The > symbol means that you need to interpret an observation. Sometimes the manual will simply provide an explanation for something you just saw. Solution Preparation Get a 250 mL volumetric flask, and rinse it thoroughly with deionized water three times. Prepare the 0.200 M KI solution: Flowchart: (Procedure outlined below.) 25.00mL of 2.00M KI(aq) 225.00mL of water burette

250mL of 0.200M KI(aq) Burettes have been set up in the lab to dispense the KI, (NH4 )2 S2 O8 , and Na2 S2 O3 solutions. Find the burette for the 2.00 M KI, and fill it with the bottle of 2.00 M KI until the solution level is a little above the top 0.00 mL mark. Drain the burette slowly into a small beaker until the solution level comes down to 0.00 mL. Remember that the top surface of the solution (the meniscus) is bowl shaped, and you should measure the level at the lower surface of this bowl. Drain the burette into the clean 250 mL volumetric flask until the solution level falls to 25.00 mL on the burette. Add deionized water to the volumetric flask until it is half full. Swirl the flask to completely mix the solution. Add deionized water until the water reaches the flask neck, and then slowly finish filling the flask up to the measurement mark on the neck of the flask. Stopper the flask, turn it upside-down, shake it for about a second, and turn the flask upright. Repeat this 9 more times.

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Pour the solution from the volumetric flask into a 500 mL Erlenmeyer flask. Be sure to seal the Erlenmeyer flask with a good-fitting stopper. Rinse the volumetric flask several times with deionized water. Prepare the 0.100 M (NH4 )2 S2 O8 solution. Use the same procedure you used to prepare the KI solution except use 1.00 M (NH4 )2 S2 O8 stock solution in place of the 2.00 M KI solution. Store this solution in a second 500 mL Erlenmeyer flask. Dont forget to rinse the volumetric flask again after you are done. Prepare the 0.00500 M Na2 S2 O3 solution. Use the same procedure you used to prepare the KI solution except use 0.0500 M Na2 S2 O3 stock solution. Store this solution in a third 500 mL Erlenmeyer flask. > For Your Information: the (NH4 )2 SO4 and KCl solutions prepared below are not actual reagents in the reaction, but they are needed to maintain the total concentration of ions in solution. Prepare the 0.10 M (NH4 )2 SO4 solution: Flowchart: 5.0 mL of 1.00 M (NH4)2SO4(aq) 45.0 mL of water Graduated Cylinder

50mL of 0.10M (NH4)2SO4(aq) Measure 5.0 mL of 1.00 M (NH4 )2 SO4 solution into a small volumetric cylinder. Pour this solution into a 50 mL volumetric cylinder. Fill the small volumetric cylinder with water and pour it into the 50 mL cylinder. Keep adding water this way until the 50 mL cylinder fills to its 50 mL mark. Pour this solution into a 125 mL Erlenmeyer flask, and swirl it for about 30 seconds. Prepare the 0.20 M KCl solution. Prepare the 0.20 M KCl solution from the 2.0 M KCl solution the same way the (NH4 )2 SO4 solution was made. Store this solution in a clean 125 mL Erlenmeyer flask.

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Solution Delivery Preparation Prepare Solution Burettes and pipette For Burette A (0.200 M KI solution): Label one burette as A. Wash burette A with water as follows: Pour about 10 mL of water into the burette. Hold the burette almost horizontally, and carefully rock it back and forth while rotate it such that the water eventually touches every part of the inner wall of the burette. Let the water drain out of the burette through the stopcock at the bottom. Wash burette A two more times with water. Wash burette A with the 0.200 M KI solution: Pour about 5 mL of the 0.200 M KI solution into the burette. Hold the burette almost horizontally, and carefully rock it back and forth while rotate it such that the solution eventually touches every part of the inner wall of the burette. Let the solution drain out of the burette through the stopcock at the bottom. Wash burette A two more times with 0.200 M KI solution. Fill burette A with 0.200 M KI over the 0.00 line. For Burette B (0.100 M (NH4 )2 S2 O8 solution): Repeat the procedure you used to wash and fill Burette A to wash and fill Burette B with 0.100 M (NH4 )2 S2 O8 . Clean and wash your 5.00 mL volumetric pipette with 0.0050 M Na2 S2 O3 solution as follows Rinse the pipette with water as follows. Repeat this a total of three times. Use the rubber bulb to draw water up to the wide part of the pipette. Quickly remove the bulb from the pipette and cover that open end with your thumb. Then turn the pipette sideways and let the solution leak (by releasing your thumb) into the wide part of the pipette.

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Slosh the solution around to rinse the entire inside. Use the rubber bulb to blow out the tip of the pipette onto a paper towel to get all the water out. Rinse the pipette with 0.0050 M Na 2 S2 O3 solution the same way you rinsed the pipette with water. Do this three times. Rinse a 10 mL graduated cylinder three times with water, and then rinse it three times with 1 mL portions of the KCl solution you made. Then label the cylinder as the KCl graduated cylinder. Rinse a 10 mL graduated cylinder three times with water, and then rinse it three times with 1 mL portions of the (NH4 )2 SO4 solution you made. Then label the cylinder as the (NH4 )2 SO4 graduated cylinder. Rinse the following with water. Just shake out the water; there is no need to dry them. A 25 mL Erlenmeyer flask labeled A A 25 mL Erlenmeyer flask labeled B A 50 mL beaker. Reaction Mixtures (Concentration Effect) For run 1: Flowchart: 1) 7.50mL of 0.200M KI(aq) (pipette) 3) 5.0mL of
2-

0.005M S2O3 (aq) 1 drops starch

2) 7.50mL of 20.100M S2O8 (aq) (pipette)

25 mL (50 mL) 4) Add KI(aq) and S O 2-(aq) 2 8 together and begin timing.

25 mL

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Use burette A to add exactly 7.50 mL of the 0.200 M KI solution to Erlenmeyer flask A: Check the solution level in the burette. Water sticks to glass such that the solution in the middle of the burette barrel seems to hang below the edges touching the glass. While looking horizontally at the hanging surface, let solution drip out of the burette until the hanging surface touches the 0.00 mL burette mark. Drain the burette into flask A until the liquid level in the burette falls to the 7.50 mL mark on the burette. Use burette B to add exactly 7.50 mL of the 0.100 M (NH4 )2 S2 O8 solution to Erlenmeyer flask B. Add to the 50 mL beaker: Exactly 5.00 mL of the 0.0050 M Na2 S2 O3 solution (use the pipette). One drop of starch indicator. Place the thermometer in the beaker, and the beaker on top of a layer of paper towels. As one of you simultaneously pours the solutions from Erlenmeye flask A and B into the beaker, the other should time the reaction from mixing. Swirl the beaker to finish mixing. Stop timing once the solution begins to turn blue. Write down the reaction time and the solution temperature. Repeat run 1. The reaction time should match the first to within 3 seconds. For run 2: use the same procedure as for run 1 using the following solutions: Add to Erlenmeyer flask A: Exactly 7.50 mL of the 0.200 M KI solution (use the burette). Add to Erlenmeyer flask B: Exactly 5.00 mL of the 0.100 M (NH4 )2 S2 O8 solution (use the burette). 2.5 mL of the 0.10 M (NH 4 )2 SO4 solution (use the 10 mL graduated cylinder) Add to the 50 mL beaker: Exactly 5.00 mL of the 0.0050 M Na2 S2 O3 solution (use the pipette). One drop of starch indicator.

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For run 3: use the same procedure except for the following changes: Add to Erlenmeyer flask A: Exactly 7.50 mL of the 0.200 M KI solution (use the burette). Add to Erlenmeyer flask B: Exactly 2.50 mL of the 0.100 M (NH4 )2 S2 O8 solution (use the burette). 5.0 mL of the 0.10 M (NH 4 )2 SO4 solution (use the graduated cylinder). Add to the 50 mL beaker: Exactly 5.00 mL of the 0.0050 M Na2 S2 O3 solution (use the pipette). One drop of starch indicator. For run 4: use the same procedure except for the following changes: Add to Erlenmeyer flask A: Exactly 5.00 mL of the 0.200 M KI solution (use the burette). 2.5 mL of the 0.20 M KCl solution (use the 10 mL graduated cylinder). Add to Erlenmeyer flask B: Exactly 7.50 mL of the 0.100 M (NH4 )2 S2 O8 solution (use the burette). Add to the 50 mL beaker: Exactly 5.00 mL of the 0.0050 M Na2 S2 O3 solution (use the pipette). One drop of starch indicator. For run 5: use the same procedure except for the following changes: Add to Erlenmeyer flask A: Exactly 2.50 mL of the 0.200 M KI solution (use the burette). 5.0 mL of the 0.20 M KCl solution (use the 10 mL graduated cylinder). Add to Erlenmeyer flask B: Exactly 7.50 mL of the 0.100 M (NH4 )2 S2 O8 solution (use the burette). Add to the 50 mL beaker: Exactly 5.00 mL of the 0.0050 M Na2 S2 O3 solution (use the pipette). One drop of starch indicator.

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Reaction Mixtures (Temperature Effect) For run 6: Add to Erlenmeyer flask A: Exactly 7.50 mL of the 0.200 M KI solution (use the burette). Add to Erlenmeyer flask B: Exactly 7.50 mL of the 0.100 M (NH4 )2 S2 O8 solution (use the burette). Add to the 50 mL beaker: Exactly 5.00 mL of the 0.0050 M Na2 S2 O3 solution (use the pipette). Three drops of starch indicator. Place the thermometer in the beaker, and warm flasks A and B and the beaker together in a hot water bath until the temperature of the beaker solution is between 30 and 35C. (The hot water from the tap should be warm enough for the hot water.) Place the beaker on top of a layer of paper towels, and use the thermometer to record the actual temperature of the solution. As one of you quickly pours these solutions into the beaker, the other should time the reaction from mixing. Swirl the beaker to finish mixing. Stop timing once the solution begins to turn blue. Write down the reaction time and the solution temperature. Average this temperature to the first, and use the average in your calculations. For run 7: Use the same procedure as in run 6 except that the solutions should be heated to about 45-50C. If the tap water is not hot enough for this, try heating some water over a Bunsen burner. For run 8: Use the same procedure as in run 6 except that the solutions should be cooled to about 10-15C in ice water. For run 9: Use the same procedure as in run 6 except that the solutions should be cooled to about 3-7C in ice water.

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Reaction Mixtures (Catalyst Effect) For run 10: Use the same procedure as in run 1 except add one drop of 0.040 M CuSO4 to Erlenmeyer flask B before starting the reaction. For run 11: Use the same procedure as in run 1 except add three drops of 0.040 M CuSO4 to Erlenmeyer flask B before starting the reaction.

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Prelaboratory Assignment
Using the data from the experimental procedure and the equations below, calculate the values in the following table.

Run [I-] [S2 O8 2-] 1 2 3 4 5 ________ ________ ________ ________ ________ ________ ________ ________ ________ ________

Recall that, M2 = M1 V1 /V2 M1 = initial concentration of KI or (NH4 )2 S2 O8 V1 = volume of solution used. V2 = the total volume of the combined solutions in the beaker

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