A Fail-Safe Kinetics Lab for A.P.

Chemistry
Presented by:
Harvey W. Gendreau, Science Department (ret.) Framingham High School, Framingham, MA 01701 (508) 877-8723 Internet: apchemtchr@aol.com

Abstract:
I have tried all kinds of kinetics labs for my Advanced Placement Chemistry classes in an attempt to determine experimentally the order of a reaction. These include iodine clock reactions (both macro and micro), thiosulfate ion and acid, hydrogen peroxide decompositions, and crystal violet decolorization using a Blocktronic on an Apple IIGS. None have given us any reliable and consistent results for the order of a reaction and its activation energy. [Kinetics labs on a microcomputer seem to lack a lot of flavor that a wet-chemistry lab gives a student. Many results come out too perfect.] This lab involves the hydrolysis of t-butyl bromide (2-bromo-2-methylpropane) in a 50/50 isopropanol/water solvent medium and the consequential titration of the HBr product with hydroxide over time. The materials are few, minimal set-up and equipment, moderate to low costs, simple data collection, and straight forward calculations. Students can easily determine the reaction order, rate constants at two different temperatures, and the activation energy. A video tape presentation will show how easily this lab can be conducted (2 trials) in a 100 minute lab session. All attendees will receive a hand out of the procedures, sample data, calculations, and materials list.
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Reaction Kinetics: The Rate of Hydrolysis of Tertiary-Butyl Bromide

Developed by: ____________________________________________________________________________
Prof. John R. Blackburn (502) 863-8102 Georgetown College Georgetown, KY 40324

Objectives: ____________________________________________________________________________
1. To explore the effect of concentration of reactants on the rate of a chemical reaction, and to learn to express this effect as the order of the reaction. 2. To determine the Rate Law for a chemical reaction. 3. To explore the effect of temperature changes on chemical reactions, and to use this effect to determine the activation energy for a reaction.

Part A. Introduction
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One important reason for the study of chemical reactions is to learn the reaction mechanism for a reaction. The reaction mechanism is the detailed sequence of steps that take place to lead to an overall reaction. Some reactant molecules that cause the molecules to rearrange and fly apart as new, reorganized molecules we call products. A more common circumstance, however, is for reactants to engage in a number of simple collisions, each leading to a different intermediate product, which continues to collide and react further (creating different intermediates) until the final products are eventually produced. Reactions are known for which as many as 20 or more different individual steps occur to lead to the final products. This sequence of steps is called the reaction mechanism. The actual sequence of individual steps (the reaction mechanism) cannot be determined by simply examining the balanced equation for the reaction. The reaction mechanism must be determined experimentally! The study of reaction rates provides important tools for the chemists use with which to deduce reaction mechanisms, through the determination of the rate law. A Rate Law is simply a mathematical expression that indicates how the rate of a reaction depends on the concentration of the various species in the overall reaction. One might have a general reaction in the form: A+2B+C2D+E
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and deduce by experiment (remember, the rate law cannot be determined by looking at the balanced equation) that the rate law has the form: rate = k[A]2[B] (eq. 1) This simply says that the rate is proportional to square of the concentration of species A, and proportional to the concentration of species B. (Note that even though species C is necessary for the reaction, its concentration does not affect the rate. This is not too unusual!) The k in the equation is simply a proportionality constant that is dependent on the particular reactants and the temperature. It is called the rate constant. The exponents on the concentration terms in the rate law are called orders; thus, the reaction above is said to be second order with respect to A and first order with respect to B. The reaction also has an overall order, which is simply the sum of the individual orders. Thus, in the example above, the reaction is a third order reaction (since 2+1=3). The study of rate laws, and in particular the determination of the individual orders of reactions, can be very helpful in deducing the reaction mechanism. One caution, however, is that the individual reaction steps in the mechanism (these are called simple reactions or elementary processes) take place at different rates. The rate law is determined ONLY by the steps leading up to and including the slowest step (this is called the Rate Determining Step), and gives NO information regarding steps that occur after the rate determining step.

Part B: What is meant by rate?

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The rate of a reaction is just how fast the concentration of some species in the reaction is changing with time. For example, if a bicycle assembler in a factory had a large stack of frames and a large stack of wheels, one could define his work rate by the rate at which frames were being used (say, 4 per hour), by the rate at which wheels were being used (this would be 8 per hour, since two wheels are required for each frame), or by the rate at which bicycles are actually being produced (which would be 4 per hour). Thus, it would not be enough to simply say he was working at a rate of four per hour without identifying what the four represented. If it represented bicycles produced, it is a faster rate than if it represented wheels used, and yet clearly there is really only one work rate that can be expressed in different terms. Rates of reaction are defined either as a rate of disappearance of reactant or as a rate of appearance of product. The rate is the change in concentration of the species divided by the time interval during which the concentration change was measured. (If 12 bicycles were produced in 3 hours, then the rate would be 12 bicycles/3 hours or 4 bicycles/hour.) Concentrations are generally used in terms of molarities, so the rate of the reaction in the example above might be defined in any one of three ways below: - change in [A] - change in [B] (a) rate = (b) rate = change in time change in time change in [D] (c) rate = change in time The minus sign in (a) and (b) is there since these rates are rates of disappearance, and thus the change in [A] or [B] is negative, whereas in (c) there is no minus sign, since this is a rate of appearance and the change in [D] is positive. Note also that the rate as defined in (a) is numerically only 1/2 that in (b) (check the balanced equation) while the rate as defined in (b) is the same as the rate as defined in (c). The rate is always defined so it is a positive number!
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Part C: The Integrated Rate Law

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Mathematics is a wonderful tool for the chemist. One can do some mathematical transformations with the rate law to develop equations that can be used to study kinetics more easily. One of these transformations makes use of the principles of calculus to develop what is called the integrated rate equation. We will look briefly at the process, but will focus on the beginning and ending forms of the equation.
figure 1 (x1,y1) a [A] p dy = m2 dx time ^ (x2,y2) m1 = y (y2 - y1) = x (x2 - x1)

In figure 1, m1 gives the average slope of the curve between points, but m 2 gives the slope of the tangent to the curve at point p, the actual slope of the curve at point p. This is a much better value than m1 gives. To understand the results, we will use two very simple rate laws one a simple first-order rate law (eq. 2) and the other a simple second-order rate law (eq. 3) as shown below (these represent two completely different chemical reactions) : (a) rate = k[A] (eq. 2) (b) rate = k[B]2 (eq. 3) Since the first rate depends only on [A], we will define the rate as the rate of disappearance of A (assume it is a reactant) . In the second case, we will define the rate as the rate of disappearance of B (also a reactant). [A] -[B] (b) rate = t t If the time interval over which the change in concentration is measured is made very small, then the concentration change during this interval will also be very small. This is analogous to making a graph of concentration vs. time for the reaction, and using points on the curve that are very close together to determine the slope of the curve. A change that is so small as to be infinitesimal, but still meaningful, is called a differential change, and is indicated with a d instead of a delta. The rate of the reaction at any point during the reaction is given by the slope of the tangent line to the curve at that point. Mathematically, this is d[A]/dt. Thus: (a) rate =

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(a) rate = (b) rate =

- d[A] = k [A] dt

(eq. 4)

- d[B] 2 = k [B] (eq. 5) dt At this point we can use integral calculus to show that eq. 4 is equivalent to eq. 6 below and eq. 5 is equivalent to eq. 7 below. The actual mathematical transformations of these equations can be found in an introductory calculus textbook. (a) ln[A] = -kt + ln[A]o (eq. 6) (b) 1 1 = kt + [B] [B] o (eq. 7)

([X]o = initial concentration of X) Two things are apparent from these transformed equations. The first is that they relate the actual concentration of the species to the time that has elapsed since the reaction began. The second is that the form of the final integrated equation depends on the initial rate law. A third thing, which is not so immediately apparent, but which is nevertheless true, is that both eq. 6 and eq. 7 are equations for a straight line. The general equation for a straight line is usually given as: y = mx + b (m = slope, b = y-axis intercept) In eq. 6, the term ln[A] is the y-variable and t (time) is the x-variable. In eq. 7, the term 1/[B] is the y-variable and t is the x-variable. Thus, if a reaction is simple first order, a graph of the natural log of concentration vs. time will be a straight line. If a reaction is simple second order, a graph of the reciprocal of concentration vs. time will be a straight line. This provides a very powerful yet simple method to determine the order of a reaction. One merely measures the concentration of the reactant as a function of time and graphs the log (or the reciprocal) vs. time to see if it is first or second order. (There are other ways of determining order this is just one method.) In this experiment, you will measure the concentration of a reactant at various times and graphically determine the order using these principles.

Part D: The Effect of Temperature on Rates of Reaction.

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Chemical reactions always proceed more rapidly at higher temperatures unless the mechanism of the reaction changes as the temperature increases. (Some biochemical reactions go more slowly at elevated temperatures, but this is because the mechanism of the reaction is affected by the increased temperature.) The famous Swedish chemist, Svante Arrhenius, studied the effect of temperature on reaction rates in the late 1800s and discovered that the rate constant of a reaction increased logarithmically in proportion to the reciprocal of the absolute temperature (remember, we said earlier that temperature affected the rate constant). This is expressed mathematically as: k = Ae-C/T (eq. 8) A and C are experimentally determined constants and T is the absolute (Kelvin) temperature. The constant C in the equation above was determined to be related to the activation energy for the reaction by C = Ea/R (Ea = activation energy and R = the gas law constant). This makes eq. 8 into:
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k = Ae-Ea/RT (R = 8.314 J mol-1K-1) (eq. 9) If the rate constant is measured at two different temperatures (k 1 at T1 and k2 at T2), then the activation energy can be determined using eq. 9 twice (the first is subtracted from the second) as: k E 1 1 ln k 2 = a (eq. 10) R T1 T2 1 In eq. 10, since the two rate constants and the two temperatures are known (have been measured), and R is a universal constant, the only unknown is the activation energy. In this experiment, you will determine rate constants at two different temperatures and use eq. 10 to determine the activation energy for the reaction.

Part E: The Actual Reaction Studied

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Todays reaction is the hydrolysis (reaction with water) of tertiary-butyl bromide (I). This molecule reacts as shown below to form the products tertiary-butyl alcohol (II) and HBr. H3C H3C H3C- C-Br + H2O H3C- C-OH + HBr
| | | |

(eq. 11)

H3C (I)

H3C (II)

As can be seen from eq. 11, each time that one tertiary-butyl bromide (tBB) molecule reacts, one HBr molecule forms. The rate of appearance of HBr is the same as the rate of disappearance of tBB. When measuring the rate at which HBr forms, we are measuring the rate at which tBB disappears. Since HBr is an acid, we can measure its presence with base, using phenolphthalein as an indicator. The greater the amount of base used, the greater the amount of HBr that has formed in the reaction.

Part F: Procedure (you will work in pairs this cannot be done alone).
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Equipment and chemicals 1. clean, dry 250 mL Erlenmeyer flask 2. clean 50 mL burette and burette clamp 3. 200 mL of a 5050 (by volume) waterisopropanol mixture 4. 75 mL of 0.20 N NaOH solution (in waterisopropanol solvent) 5. phenolphthalein in a dropper bottle 6. tertiary-butyl bromide, tBB (your instructor will deliver this) 7. clock or watch with second hand for timing (a stopwatch is great!) 8. ice bath Directions for Experiment Place 100 mL of the waterisopropanol solvent (this is used so that the tBB will dissolve - it is not soluble in water alone) into the 250 mL Erlenmeyer flask and add approximately 15 drops of phenolphthalein to the solvent. Place the flask into
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the ice bath and chill the solvent until the temperature stabilizes around the ice point. You must keep a good deal of ice in the ice bath throughout the experiment - the temperature must not rise! While the solvent is cooling, rinse and fill your burette with the 0.20 N NaOH solution. It will be advantageous to have the initial reading be 0.00 mL. [Dont forget to eliminate the air bubbles from the tip before taking the initial reading.] When the solvent has completely chilled and you have recorded an initial reading (0.00 mL), run about 2 mL of base into the flask (keep the flask in the ice bath) and read the burette. Then ask your instructor to add the tBB to your flask (it should be pink at this time). Record the exact time when the tBB is injected into your flask. Gently swirl the flask to mix the contents and allow the flask to sit in the ice bath and observe the color. Swirl the flask from time to time to keep it thoroughly mixed. Record the exact time when the flask changes from pink to colorless. Then, without changing anything else, add another 2 mL portion from the burette (the solution should become pink again) and record the burette reading. Again watch the flask and record the exact time when the flask becomes colorless. Repeat this process until you have made a total of 7 additions of NaOH. For the last 3 additions, you may add 1.5 mL of NaOH rather than 2 mL. The only data that you need to record during this time are (1) the actual burette readings, and (2) the actual clock times when the solution becomes colorless. You do not need to record the time when the NaOH is added from the burette. After the solution has become colorless after the 7 th addition of NaOH, remove the flask from the ice bath. Fill a large beaker about 1/4 full with tap water and set up a hot water bath for 10 minutes at a temperature between 6080 C. Then remove the flask and cool the flask and contents to room temperature (you may use tap water running over the bottom of the flask). Place the flask under the burette before beginning the titration. Begin with the final reading taken earlier. The volume you are looking for is the total base added during the experiment, not just the amount added after heating the flask! Do the entire experiment a second time, this time eliminating the ice bath. The reaction this time will take place at room temperature. Follow the directions exactly as before. Warning: The reaction goes much more rapidly at the higher temperature. If you set up a second burette, you can do the addition of base while the flask from part I is in the hot water bath. You must be ready to work quickly! (Dont use the same burette that you are using for #1 since you want to continue addition to #1 from the point where you stopped before heating it.) After taking your last time reading, put this flask in the water bath, cool, and titrate to a final endpoint as you did with #1.

Part G: Calculations
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To understand the calculations, we first must understand that the rate of this reaction depends in some way on the amount of tBB still remaining in the flask at any particular time, rather than the amount that has reacted. We must be able to use the information we have collected to produce numbers that vary in the same fashion as the concentration of tBB remaining at any time. The final titration for each run provides a very important bit of information the total base needed to neutralize all the HBr produced in the reaction. (Heating
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the flask to 70 for 10 minutes caused the reaction to go essentially to completion.) This is directly proportional to the total amount of tBB that was present in the flask at the start of the reaction (Ao). This amount of base is designated b, and is a constant number that depends on how much was initially injected into your flask. This number is called the infinity reading because it is the base required if the reaction proceeds for an infinite time. The burette readings for each addition (which are designated b t) represent the total base added to the flask at any time. This is proportional to the total amount of tBB that has reacted at each point (when the solution becomes colorless). Thus we can get a measure of how much tBB still remains in the flask by calculating how much base has not yet been added, or the expression (b - bt). We also need the volume of the solution at any time, since the rate depends on the concentration of reactant, rather than just on the amount present. As we add base during the reaction, the volume changes, so we need to calculate the new volume at each point along the way. If Vo represents the initial volume (100 mL in this reaction), then (Vo + bt) gives the total volume at any time. We now have an expression for tBB remaining at any time (b - bt) and an expression for total volume at the same time (V o + bt). Since concentration is amount/volume, we can divide these two expressions to get the tBB concentration at any time. (This doesnt give the true concentration, but gives a number that behaves exactly like the concentration, thus it can be treated graphically.) In summary, the expressions below are used in calculations: Symbol b bt (b bt) Vo (Vo + bt) (b bt) / (Vo + bt) Represents total amount of tBB injected into flask (a constant) total amount of tBB that has reacted at time = t total amount of tBB remaining in flask at time = t initial volume of solution (100 mL in this case) total volume of solution at time = t concentration of tBB remaining in solution at time = t
(The symbol H will be used for this term.)

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For discussion purposes, we will let the letter H represent the last term in the list above - namely the concentration of tBB at time = t. The rate of the reaction depends on this number in some way (the reaction is either simple first order or second order). This means that either eq. 6 or eq. 7 is the correct equation for this reaction. We determine which equation is correct by making two graphs: one of lnH vs. time and the other of vs. time (see discussion on page 2 and 3). The graph that is the straight line tells us the order of the reaction. Once we find the correct graph (and order), we can determine the actual rate constant from the slope of the line (m = k in the two equations). Prepare two graphs for the data at each temperature (a total of 4 graphs) . At each temperature, make one graph of lnH vs. time and a second graph of 1/H vs. time. Choose which graph is the best straight line, and measure the slope of the line (this is the rate constant k) . You will now have two rate constants at two temperatures. Use this data in eq. 10 to calculate the activation energy for the reaction. Use the value of R listed by eq. 9, remembering to use absolute or Kelvin temperature.

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Name____________________ Partner__________________ Lab Date_________ Date Submitted__________

Reaction Kinetics: The Rate of Hydrolysis of Tertiary-Butyl Bromide

Raw Data - Cold
temperature of solution in ice bath:

Raw Data - Room Temperature

temperature of solution:

burette reading clock reading total elapsed burette reading clock reading total elapsed (mL) when colorless time (sec.) (mL) when colorless time (sec.) (injection) (injection) 0.00 0.0 0.00 0.0

final volume

-----

final volume

-----

ANALYSIS OF DATA

H= C ( K)

Cold temp. of solution in ice bath: b (infinity reading): mL elapsed time (t) 0 base added (bt) 0.00

(b bt)

(Vo + bt) 100

ln H

infinity

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Room Temperature temp. of solution : b (infinity reading): elapsed time (t) 0 base added (bt) 0.00 C ( mL (b bt) (Vo + bt) 100 H ln H K)

infinity

k1 = ________ k2 = ________order = _____ Eact = ____________

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Instructors Notes Stockroom Needs

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1. Chemicals: 50/50 isopropanol/water mixture (by volume) - Each pair of students will need about 300 mL total of this, part of which is in the form of an NaOH solution described below. From experience, there is a little more waste than usual with this experiment, so about 5 Litres should be prepared for each lab of 25-30 students. About 2/3 of the solution should be water-isopropanol solvent. These liquids tend to mix slowly when combined, so the mixture will need to be thoroughly agitated for a good while after the water and isopropanol are combined. [Drug store rubbing alcohol is 70% isopropyl alcohol and water. By mixing 300 mL of water with 700 mL of rubbing alcohol, the suitable solvent may be made. Although the author sees no apparent problem, he has not tested the experiment in this less expensive manner. Please report your results if you should attempt it.] 0.2 N NaOH solution in 50/50 water/isopropanol solvent - About 1/3 of the above solvent is used to prepare the NaOH solution, at the rate of 8 grams NaOH/L of solvent. Using the actual solvent to prepare the NaOH solution insures that no change in solvent characteristics takes place when base is added to the flask during the experiment. phenolphthalein - One fairly large dropper bottle in each lab should be sufficient each pair of students will use 30-40 drops (about 2 mL). t-butyl bromide (tBB) - This will need to be ordered (possibly cataloged as 2bromo-2-methylpropane or 2-methyl-2-bromopropane; Sigma-Aldrich Chemical Co, Milwaukee). This tends to decompose easily, so the supply needs to be fresh. I would suggest buying a 50 g or 100 g bottle (25 g is better if available). A lab of about 26 students will use about 15 grams of this (it is dispensed by the instructor with syringes or marked Beral pipettes, so not much waste occurs). Each kinetic run requires an injection of 0.5 cm 3 of tBB and each pair of students does 2 runs. 2. Apparatus: 50 mL burettes - It would be good if there were one burette per student (two per pair), or about 26 burettes per lab - maybe a few extra so leaking burettes can be replaced. It would be impossible to do this experiment if the burette leaks! ring stand/iron ring/wire gauze - One setup per pair of students. -10 to 110C thermometers - One per pair. disposable syringes - Small (3 cc) disposable plastic syringes of the type sold to diabetics in drug stores are used. These will be used by the instructor for dispensing the tBB. Since the tBB chews up the plastic a bit, they cannot be reused for a second lab period and should be destroyed after each lab. 3. Other: ice bath - Each pair of students will need a large beaker full of ice, possibly a little more. References
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Shakhashiri, Bassam Z., Chemical Demonstrations, Volume 4, 10.7 Hydrolysis of 2- 11 -

Chloro-2-Methylpropane, University of Wisconsin Press, Madison, 1992.

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0.18

0.16

O O O O

0.14

concentration vs. time @ 297K

R 2 ! 0.886

0.12

[concentration]

0.1

0.08

O O

0.06

0.04

0.02

O O

100

200
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300

400

500

600

time (sec.)

"1.5

"2

#n (concentration) O vs. time O @ 297K O

O O
$(%) ! "0.004370&% "1.840 R 2 ! 0.9998

"2.5

#n (concentration)

"3

"3.5

O
"4

"4.5

O
0 100 200 300 400 500

time (sec.)
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90

80

70

60

1 concentr ation vs. time @ 297K

R 2 ! 0.8986

50 40

30

20

O O O O
0

10

100

200

300

400

500

60

time (sec.)
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0.18

0.16

concentration O vs. time @ 276K

O

0.14

0.12

O R = 0.9585
2

0.1

0.08

O O O

0.06

0.04

O
0 500 1000 1500 2000

time (sec.)
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22

20

18

16

1 concentr ation vs. time @ 276K O

R = 0.9811 O
2

14

12

10

O O O

6O 0

500

1000

1500

2000

time (sec.)
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O O

#n (concentration) vs. time @ 276K

O f(x) = -0.0005399*x -1.826 O

"2.2

R = 0.9982
"2.7

O O O
"3.2 0 500 1000 1500 2000 2500

time (sec.)
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