USM Chemistry Workshop

CHY 115

Science is the tool of the Western mind and with it more doors can be opened than with bare hands. C.G. Jung

Unit K1 Chemical Kinetics: Concepts and Models

f we search for a definition of chemistry, it would likely refer to the transformations of matter. An example would be something similar to the study of substances and how they react when in contact with one another. You have witnessed countless chemical reactions throughout your life, and undoubtedly you have observed that some occur very quickly, such as when wood burns in a fireplace, and others occur very slowly, such as when the iron body of a car rusts. The study of the rates of chemical reactions and how they take place forms a subdiscipline within chemistry known as chemical kinetics. Perhaps you have a bottle of hydrogen peroxide in your bathroom cabinet. It is usually stored in a brown bottle, and its label will have the instructions store in a cool, dark place. These storage instructions are there because hydrogen peroxide undergoes a decomposition reaction, forming water and oxygen. Fortunately, the reaction is slow enough that your bottle will last for a few years. If you were to sprinkle in some solid manganese dioxide, however, the contents of the bottle would completely decompose in a matter of seconds. Remarkably, all of the manganese dioxide could be filtered off from the remaining water and reused to speed the decomposition of another bottle of hydrogen peroxide. Substances such as manganese dioxide, which speed up a chemical reaction without being consumed in the reaction, are called catalysts. The process of life itself depends on catalytic molecules known as enzymes. Most biochemical reactions rely on enzymes which increase the rate of the reaction by 1,000 to 100,000,000,000,000,000 times when compared with the uncatalyzed reaction. An even more remarkable property of enzymes is that they produce reaction products at near-100% yields, allowing all of the reaction energy to be used by the cell as well as virtually eliminating any undesirable by-products. No matter the type of chemical change that you may considerburning, rusting, decomposition, biological reactions, or any other transformationyou can see that an understanding of the reaction kinetics is essential to comprehending the process.

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Average and Instantaneous Rate

You arrive at school one day, and as you wait for your first class to begin, your friend arrives, sits next to you, and remarks, It was a slow commute today. You ask, How fast did you travel? Your friend looks back at you with a puzzled look in her eyes. How do you respond to someone who asks about the speed of a trip? If the distance from home to school is ten miles and it takes a half hour to make the trip, your average speed, or average rate of travel, is 20 miles per hour. However, along the way you may have gone as fast as 45 mph, but at other times you were stopped. Your speed at any given instant, your instantaneous rate, is shown by your speedometer reading at that moment. Clearly, there are two ways of expressing rates, your choice of which depends on the type of information that is needed. The rate of a chemical reaction is defined as the change in concentration of a reactant or product of that reaction per unit time. This can be expressed as . Just as with the speed of a trip from home to school, chemical reaction rates can be average or instantaneous. To obtain an instantaneous rate, the reaction needs to be examined over a time period small enough to ensure that the reaction has proceeded only slightly.

Rate Laws
A rate law describes how the reaction speed depends on the concentrations of reactants and products. It is determined from experiments that measure the change in concentration of one or more of the reactants or products over time. Consider the following rate laws that can apply to the general reaction A + B Products: rate = [ A] = k [A] t = k [A]2 (K1.1)

[ A] rate = t rate =

(K1.2)

[ A] = k [A] [B] t [ A] = k t

(K1.3)

rate =

(K1.4)

Equations K1.14 express the rate of the reaction in terms of the disappearance of A, [ A] rate = . This rate is proportional to the molar concentration of A and/or B, raised to a t power. In each case, the proportionality constant is given by k, which is known as the rate constant.

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The term reaction order is used to refer to the exponents of the concentrations. We can refer to the overall reaction order, the sum of the exponents of all of the reactants, or the reaction order of a particular reactant, the exponent of that reactant. For example, the rate law in Equation K1.2 is said to be second order with respect to A. For Equation K1.3, the reaction is second order overall and first order for each of the reactants. It is important to note that the order of the reaction does not necessarily follow from the reaction stoichiometry. The rate laws we have seen so far express the relationship between rate and concentration. Another form for expressing rate laws is to show the relationship between concentration and time. These are called integrated rate laws. The chart below shows the differential rate law, the type we first introduced, and the corresponding integrated rate law for zeroth, first, and second order reactions. Differential Rate Law rate = -k rate = -k[A] rate = -k[A]2 Integrated Rate Law [ A]=[ A]0 kt [ A]=[ A]0e - kt 1 1 = kt [ A] [ A]0

The rate constant can be expressed in an alternate form known as the half-life of the reaction, which is defined as the time needed for the reactant concentration to fall to exactly half of its original concentration. Half-lives are most commonly used for first-order reactions. The relationship between the half-life and the rate constant for a first-order reaction is given by 1/2= ln 2 k (K1.5)

Reversibility
It is often the case that the rate of reaction will depend not only on the reactant concentrations but also the product concentrations as well. For example, the experimentally-determined rate law for the reaction k1 A B k2 may be rate = k1 [A] + k2 [B] (K1.6)

In this case, the reaction is said to be reversible. You will see that kinetic reversibility is closely connected with the concept of equilibrium.

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Self Test
1. Which of the following statements express an instantaneous rate and which express an average rate? a) It took 58 minutes to drive to work today. b) A car traveled 1.00 foot in 0.01 second. c) A compound fully decomposed in 0.001 second. d) A compound is 3.0% decomposed in 0.05 second. For each of the following rate expressions, state the order of reaction with respect to B. a) rate = k [A] [B] b) rate = k [A] [B]2 c) rate = k Consider the following plot of reactant concentration versus time:

2.

3.

Reaction Rate
0.0100 0.0080 0.0060 Concentration (M) 0.0040 0.0020 -0.0000 0 10 20 Time (s) 30 40 50

a) What is the rate of reaction between 8 and 12 seconds?

b) What is the rate of reaction over the first 36 seconds? c) Which of the two rates, Part (a) or (b), would be regarded as a better estimate of an instantaneous rate? Explain your choice.

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USM Chemistry Workshop

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Workshop: Chemical Kinetics: Concepts and Models

Questions 1 and 2: Work in pairs or groups of three, as directed by your leader. 1. Consider a simple chemical reaction, A B, that follows a first-order rate law, rate = k [A]. You will model this reaction with pennies. Start with 100 pennies, which will represent the initial concentration of A, 100 mM. Each penny will therefore represent 1 mM. Student A (SA) will represent the concentration of A, and Student B (SB) will represent the concentration of B. We will represent the reaction of A to form B by passing pennies from SA to SB. Each exchange of pennies will represent one second of time. SA will do the physical manipulation of the pennies, and SB will record the results. If you are in a group of three, the third person should verify the calculations and record the results. We will model a reaction in which 10% of the concentration of A reacts per second. Thus for each exchange (each second), SA should transfer 10% of the remaining pennies to SB. Round fractions to the nearest penny. Continue this exchange for 15 seconds. Record concentrations of A and B (number of pennies) each second (after each exchange step) in the table below. Leave the ln [A] column blank for now. Time (s) 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 [A] (mM) 100 [B] (mM) 0 ln [A] 4.61

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Plot the concentration of A versus time on the graph below. Use a different color to plot the concentration of B versus time on the same graph.

Calculate ln [A], and record the data in the table. Plot ln [A] versus time on the graph below.
ln [A] vs. Time for A 5 B

ln [A]

0 0 5 Time (s) 10 15

Determine the slope of the best-fit straight line for the plot of ln [A] vs. time. How does this slope relate to the fact that 10% of A reacted per second?

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Lets apply the modeling technique developed in Question 1 to a reversible reaction, A B a) In each second (exchange step), allow 10% of A to react to form B, then allow 10% of B to react to form A. Record the results in the first two columns of the table below. b) In each second (exchange step), allow 10% of A to react to form B, then allow 5% of B to react to form A. Record the results in the last two columns of the table below. Time (s) 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 10%/10% [A] (mM) 100 [B] (mM) 0 10%/5% [A] (mM) 100 [B] (mM) 0

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Plot the concentration of A versus time for the 10%/10% reaction on the graph below. Use a different color to plot the concentration of B versus time on the same graph.
Concentration vs. Time for A
.

100

Concentration (mM)

50

0 0 5 Time (s) 10

15

Plot the concentration of A versus time for the 10%/5% reaction on the graph below. Use a different color to plot the concentration of B versus time on the same graph.
Concentration vs. Time for A
.

100

Concentration (mM)

50

0 0 5 Time (s) 10

15

K1.8

USM Chemistry Workshop 3.

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The civilization on the planet Ecton is endangered by the continual illegal disposal of Klingon hair spray which is causing the atmosphere to decompose by a first-order rate law. Science Officer Spock has determined that their atmosphere is decomposing with a halflife of 12.50 min1. Dr. McCoy, the medical officer, has determined that the Ectonians need a minimum of 6.25% of the original atmosphere to survive. Meanwhile, Scottie, the chief engineer, is desperately trying to fix the transporter so that the entire Ectonian population can be transported to a safe planet. You are the acting Commander, replacing Captain Kirk, who is on vacation. How long does Scottie have to repair the transporter?

4.

What are the units for zeroth, first, and second order rate constants? Use moles, liters, and seconds as the basic units.

K1.9

USM Chemistry Workshop 5.

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The following initial rate data was collected for the reaction of hydrogen iodide with ethyl iodide: HI(g) + C2H5I(g) C2H6(g) + I2(g) [HI] 0.015 0.030 0.030 [C2H5I] 0.900 0.900 0.450 Initial Rate (mol/L . s) 4.01 105 8.04 105 3.99 105

From the data, determine the rate law and the value of the rate constant.

6.

You are assigned to a team that is conducting research on the decomposition of a protein in the presence of an oxidizing agent while in aqueous solution. As the kinetics expert on the team, your job is to determine the rate law for the reaction. You have available a spectrophotometer that can measure the concentration of the protein at any concentration above a minimum of 0.1 mM. Describe the experiments you will perform.

K1.10

USM Chemistry Workshop 7. Reconsider the plot shown in Self Test Question 1: This plot shows a first order decay with an initial concentration of 0.010 M

CHY 115

Reaction Rate
0.0100 0.0080 0.0060 Concentration (M) 0.0040 0.0020 -0.0000 0 10 20 Time (s) 30 40 50

. Estimate the initial rate.

Estimate the rate constant.

Estimate the half-life from the rate constant.

Is the estimated half-life consistent with the plot?

K1.11