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Weeks 2 & 3 Chemical Kinetics

Life is change. How it differs from the rocks.


Paul Kantner Songwriter

Chemical kinetics is one of the more difficult topics covered in a general chemistry course. One of the reasons is that it involves non-linear algebraic relationships. This two-week experiment is designed to help you to better understand chemical kinetics, to sharpen your solution-making technique and to improve your observational skills. You will be asked to apply the concepts you have been learning about in lecture to a lab problem. The reaction you will investigate involves the bleaching of a fabric dye with common household bleach (sodium hypochlorite, NaOCl). The change in dye concentration will be monitored with a spectrophotometer. The only other equipment required is volumetric glassware (to make the solutions) and a timepiece. The precision obtained when performing the experiment will depend on the accuracy of the timepiece, your skill using it, your skill using a spectrophotometer, and the accuracy with which the solutions are made. Educational Objectives: A student who has successfully completed this experiment will be able to design a procedure for collecting kinetic data, accurately perform quantitative dilutions, use a spectrometer to monitor concentration during a kinetic experiment, collect time vs concentration data, use the results of one trial to modify concentrations for the next, and use experimental data to determine a rate law for a reaction. Experimental Objectives: A student who performs this experiment is asked to collaborate with others to develop a procedure for performing a reaction and collecting absorbance vs time data, run a reaction a number of times using different concentrations of reactants, and evaluate the data from the reactions to determine a rate law for the reaction.

Background
One of the more valuable tools for the characterization and understanding of chemical reactions is the measurement of reaction rates. The rate at which a chemical reaction proceeds can be critical. For example, the strength of concrete is determined by the rate at which it sets. Understanding what controls this rate is critical to the reliable manufacture of strong concrete. Clinical testing is another area where reaction rates are measured. Many clinical tests involve measuring the rate of a reaction catalyzed by an enzyme. The rate is directly proportional to the amount of enzyme present. An example is the Lactate Dehydrogenase test. When an organ is damaged, it dumps large amounts of this enzyme into the blood. The test measures the rate of the reaction mediated by this enzyme. An increased rate indicates an unusually large amount of the enzyme in the blood, a strong indication of damaged tissue. Liver damage and heart muscle damage (as from a heart attack) are two of the more common ailments assessed using kinetic tests.

Kinetic Experimentation
Chemical kinetics is the study of the progression of chemical reactions over time. Reactions do not occur instantly. They take time. Some occur fast (explosions). Others are slow (rusting). The rate of a chemical reaction is defined as the rate of change in the concentration of a reactant (d[reactant]) or a product (d[product]) over time (dt). rate =
d[product] dt

If all three molecules (two hydrogens and one oxygen) participate in the rate-determining step, then the rate law will be rate = k[H2][H2][O2] (2-3) Notice that the hydrogen concentration term appears twice. This is because there are two hydrogen molecules involved in the reaction. In this case, the rate law can be simplified to rate = k [H2]2 [O2] If the rate determining step involves only one molecule of hydrogen, then the rate law will be rate = k[H2] (2-5) (2-4)

The reaction rate can depend on the amount of each reactant present, the temperature and the presence of a catalyst. The rate does not normally depend on the amounts of products made. The interplay of these variables is normally expressed as a rate law for a given reaction. In a rate law the rate is set equal to a constant, k, multiplied by the concentrations of all the reactants that participate in the rate-determining step. The constant (k) incorporates the effects of both temperature and catalysts and is, therefore, only constant if the temperature and catalysts are constant. Consider the reaction of hydrogen gas and oxygen gas to make water 2 H2 + O2 2 H2O (2-2)

d[reactant] dt

(2-1)

And there are other possibilities. Since the overall reaction does not describe the rate-determining step, rate laws cannot be predicted from overall reaction equations. They must be determined experimentally. This is done by measuring the rate of reaction at different concentrations and seeing what form of the rate equation fits the data. This is what you are expected to do in this experiment. The first step is to determine which reactants to include and how many of each. If we were to perform the water synthesis reaction at different oxygen concentrations (keeping [hydrogen] constant) and observe that the rate of the reaction did not vary, then we could conclude that the rate law does not include oxygen. The number of each reactant involved in the rate equation is referred to as the order of the reaction with respect to that reactant. This is also the power that needs to be applied to that concentration term in the rate law. In our example where the rate does not depend on [O2] the order with respect to O2 is zero and the oxygen term in the rate law is [O2]0.

Figure 2-1. Plot of kinetic experimental data. Assume in our example that changing the oxygen concentration does change the reaction rate. Then we need to determine exactly how many oxygen molecules are involved. The order could be one, or two, or even some higher integer. There are two ways to do this. The first is by proportionating. We would measure reaction rates at different oxygen concentrations (again, keeping [H2] constant) and see how they relate. If doubling the oxygen concentration doubled the rate, then the reaction is first order. If doubling the oxygen concentration quadrupled the rate, then the reaction is second order. Mathematically this is demonstrated by Equation 2-6. rate = [O2]n (2-6) If the rate doubles when [O2] doubles, then the value of n must be one. If the rate quadruples when [O2] doubles, then the value of n must be 2. The charm of this method is that it can be done with just a few measurements. The limitation is that it is highly susceptible to experimental error. The other way to determine the order of a reaction is to use the integrated rate equations. In this case data is plugged into the integrated rate equations and plotted. The equation that produces a linear plot gives you the order of the reaction. This method requires lots of data but produces much more reliable results. The integrated rate equations can be obtained from any general chemistry text. There are three major issues to address when doing kinetic experiments. The first is determining the rate of the reaction. If the rate depends on the concentration of the reactant and the reactant is being consumed, then the rate will change as the reaction progresses. The rate then must be measured at any given instant along with the concentrations of the reactants. Which brings us to the second major issue. How are the concentrations of the reactants to be monitored? Unless some probe is available to measure instantaneous concentrations the amounts of reactants can only be estimated based on the amounts originally mixed. The best probe for measuring concentrations is absorption spectroscopy. Beers law allows us to measure absorption values and easily convert them into concentrations as long as we have accurate values for the molar absorptivity and cuvet path length. A reaction is begun in a cuvet and placed in the spectrophotometer. The absorbance is measured along with the time. The results are plotted to obtain a graph like the one in Figure 2-1. Remember that the rate is the change in concentration with time (Equation 2-1). This can be approximated by measuring differences over short intervals. d[product] [product] rate = = (7)
dt t

Rates are obtained from a reaction plot by drawing tangents to the plot at particular concentrations and then determining the slope of that tangent. That slope is the rate for that concentration. A rate can be determined at any point where a tangent can be drawn. The third issue to consider is keeping all the other reactants constant. On the surface this seems to be a difficult problem. How can a reactant concentration be kept constant if it is being consumed in the reaction? The answer is to make the amount of reactant consumed insignificant in terms of the total concentration. By using a large excess of the reactant to be controlled, it is possible to assume that the concentration is constant with some certainty. A large excess would be 1000 times what is expected to be consumed. You will be investigating the bleaching of a fabric dye by sodium hypochlorite, NaOCl. Bleaching is the process of removing color. A bleaching reaction is one that converts a colored molecule into a colorless molecule, typically through the oxidative breaking of a double bond. While many different chemicals can bleach dyes, NaOCl is the chemical most commonly referred to as bleach.

Figure 2-2. Allura Red, a food dye (FD&C #40) The dyes you will work with are complex organic molecules that owe their color to a particular arrangement of double bonds known as conjugation. While the action of a bleach on a dye is quite complex, the step that results in the disappearance of color is usually rather simple. Breaking one bond in the organic molecule is often sufficient to destroy the molecules ability to absorb light in the visible region.

The Problem
Your group will be assigned a set of four dyes to evaluate. The idea is for each member of the group to be responsible for one of the dyes. But you are to work together as a group to collect data on all four dyes. You are to determine the rate law for the bleaching of each dye with sodium hypochlorite, NaOCl. This involves performing the reaction and measuring the change of concentration over time. This data will be used to determine the order of the reaction with respect to both dye and bleach and then determining the rate constant, k. This experiment generates a considerable amount of data. It is very time consuming to do the calculations by hand. The use of Excel to crunch the numbers is highly recommended.

Procedure
The following materials will be available for your use. Concentrated solutions of dyes. Household bleach. The normal concentration of a household bleach (sodium hypochlorite, NaClO) is between 5 and 7 % (W/V). The exact value will be on the label.

Red Tide Spectrometers. A volumetric glassware kit and the contents of your locker. Initial Reaction. Bleaching a dye is easy to do. To gain a feel for the reaction, put a few mLs of the dye solution in a beaker or test tube and add a few mLs of the stock bleach solution. Observe the reaction and note how fast it goes. Heres a short video clip that demonstrates the basic reaction (http://youtu.be/QXHVZv4SjeA).

Data Collection. Using the plan you and your group have agreed upon generate a kinetic plot. Plot the results. Inspect your kinetic plot and determine what changes need to be made for the next run. Consider the following. a. Did you do a good job of mixing the reactants? b. Did you collect data for long enough? Too long? c. Should the concentrations of any of the reactants be changed? Make any new solutions required and continue generating kinetic plots until you have sufficient data at various dye and bleach concentrations to complete your analysis.

Data Analysis and Report Considerations


At the end of the experiment you should have many kinetic runs. Some of these will not be of any value. You need only work up those trials that provide useful data. For each reaction you choose to evaluate you will need to generate a table containing times, dye concentrations and bleach concentrations. The dye concentrations can be calculated from the absorbance measurements. Since the bleach concentration should be large enough to be considered constant, it can be included as a statement at the top of the table. This table will also have to include calculated reaction rates at selected dye concentrations.

Figure 2-3. Determining rates from raw data. Calculating instantaneous rates is done by calculating the slope of the tangent to the curve at a particular dye concentration. This is most easily done by selecting data points on either side of a data point and calculating the slope between those two points. Consider Figure 2-3. To determine the reaction rate at point p2, a tangent at that point is needed. This can be approximated by calculating the slope between points p1 (coordinates x1 and y1) and p3 (coordinates x2 and y2). Chapter 2 contains an example of how to determine a slope from point coordinates. All of this is a lot of calculating. Much time can be saved by entering your data in Excel or an equivalent spreadsheet and putting in formulas to calculate the needed quantities.

Because you can calculate a rate for every dye concentration in your reaction you will have a very large number of data points for determining the order with respect to your dye. You can select certain dye/rate values and use the proportionating method. But since you have such a large number of values it is recommended that you use the integrated rate equations. Again, if you use a spreadsheet program you can put in the formulas to calculate the integrated rate values. You should do this for both the first order and second order equations. The one that produces a linear plot will correspond to the order with respect to your dye. Unfortunately, you will have a limited amount of data for determining the order with respect to bleach. Since each reaction was performed at a constant bleach concentration, you can get only one bleach point from each reaction. Two different reactions run at different bleach concentrations are the minimum required data. By selecting rates at the same dye concentrations for different reactions at different bleach concentrations you can use the proportionating method to determine the order with respect to the bleach. Finally, you will need to calculate the value for the rate constant, k. This can be done for every rate you determined from every trace. Again, you will have many data points. Use the rate value and the concentrations of dye and bleach that correspond to that rate to determine a value of k. Do this for a large number of the more reliable data points. Average these k values and then compute a standard deviation as described in chapter 2 of the technique book. Use the standard deviation to evaluate the precision of your data. Again, if you use a spreadsheet program the formulas can be entered and k calculated quite quickly.