Fail Safe Kinetics Lab

8/13/2019 Fail Safe Kinetics Lab

1/19

A Fail-Safe

Kinetics Lab

forA.P. Chemistry

Presented by: Harvey W. Gendreau, Science Department (ret.)

Framingham High School, Framingham, MA 01701

(508) 877-8723 Internet: [email protected]

Abstract:

I have tried all kinds of kinetics labs for my Advanced Placement Chemistry classes in an attempt to deter-mine 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 aBlocktronic 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-chemistrylab 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/watersolvent medium and the consequential titration of the HBr product with hydroxide over time. The materials arefew, minimal set-up and equipment, moderate to low costs, simple data collection, and straight forwardcalculations. Students can easily determine the reaction order, rate constants at two different temperatures, andthe activation energy.

A video tape presentation will show how easily this lab can be conducted (2 trials) in a 100 minute lab ses-sion. 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 BromideDeveloped by:

____________________________________________________________________________

Prof. John R. Blackburn Georgetown College

(502) 863-8102 Georgetown, KY 40324

Objectives:

____________________________________________________________________________

1. To explore the effect of concentration of reactants on the rate of a chemicalreaction, 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 touse this effect to determine the activation energy for a reaction.

Part A. Introduction______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________ One important reason for the study of chemical reactions is to learn the

reaction mechanism for a reaction. The reaction mechanism is the detailedsequence of steps that take place to lead to an overall reaction. Some reactantmolecules 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 adifferent 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 stepsoccur to lead to the final products. This sequence of steps is called the reaction

mechanism. The actual sequence of individual steps (the reaction mechanism)cannotbe determined by simply examining the balanced equation for the

reaction. The reaction mechanism must be determined experimentally! Thestudy of reaction rates provides important tools for the chemists use with whichto deduce reaction mechanisms, through the determination of the rate law.

A Rate Law is simply a mathematical expression that indicates how the rate ofa reaction depends on the concentration of the various species in the overallreaction. One might have a general reaction in the form:

A + 2 B + C 2 D + E

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and deduce by experiment (remember, the rate law cannot be determined bylooking 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 ofspecies A, and proportional to the concentration of species B. (Note that eventhough species C is necessary for the reaction, its concentrationdoes not affectthe rate. This is not too unusual!) The k in the equation is simply a

proportionality constant that is dependent on the particular reactants and thetemperature. It is called the rate constant. The exponents on the concentrationterms in the rate law are called orders; thus, the reaction above is said to besecond order with respect to Aandfirst order with respect to B.The reaction alsohas an overall order, which is simply the sum of the individual orders. Thus, inthe example above, the reaction is a third order reaction (since 2+1=3). The studyof rate laws, and in particular the determination of the individual orders ofreactions, can be very helpful in deducing the reaction mechanism. One caution,however, is that the individual reaction steps in the mechanism (these are calledsimple reactionsor elementary processes) take place at different rates. The ratelaw is determined ONLYby 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?______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________

The rate of a reaction is just how fast the concentration of some species in thereaction is changing with time. For example, if a bicycle assembler in a factoryhad a large stack of frames and a large stack of wheels, one could define his workrate by the rate at which frames were being used (say, 4 per hour), by the rate atwhich wheels were being used (this would be 8 per hour, since two wheels arerequired 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 simplysay he was working at a rate of four per hour without identifying what the fourrepresented. If it represented bicycles produced, it is a faster rate than if itrepresented wheels used, and yet clearly there is really only one work rate thatcan be expressedin different terms. Rates of reaction are defined either as a rateof disappearance of reactantor as a rate of appearance of product. The rate is thechange in concentration of the species divided by the time interval during whichthe 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 aregenerally used in terms of molarities, so the rate of the reaction in the exampleabove might be defined in any one of three ways below:

(a) rate =

- change in [A]

change in time (b) rate =- change in [B]

change in time

(c) rate =change in [D]

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 minussign, since this is a rate of appearanceand the change in [D] is positive. Note

also that the rate as defined in (a) is numerically only 1/2 that in (b) (check thebalanced 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______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________

Mathematics is a wonderful tool for the chemist. One can do somemathematical transformations with the rate law to develop equations that can beused to study kinetics more easily. One of these transformations makes use of theprinciples of calculus to develop what is called the integrated rate equation. Wewill look briefly at the process, but will focus on the beginning and ending forms

of the equation.

figure 1

[A]

time

dy

dx=m2

m1= y

x=

(y2-y1)

(x2-x1)

p

^

a

(x1,y1)

(x2,y2)

In figure 1, m1gives the averageslope of the curve between points, but m2gives the slope of the tangent to the curve at point p, the actualslope of the curveat point p. This is a much better value than m1gives.

To understand the results, we will use two very simple rate laws one a simplefirst-order rate law (eq. 2) and the other a simple second-order rate law (eq. 3) asshown 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 ofdisappearanceof A (assume it is a reactant). In the second case, we will define therate as the rate of disappearanceof B (also a reactant).

[A] - [B](a) rate (b) rate =

t t

=

If the time interval over which the change in concentration is measured is madevery small, then the concentration change during this interval will also be verysmall. This is analogous to making a graph of concentration vs. time for thereaction, 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 stillmeaningful, is called a differentialchange, and is indicated with a d instead of adelta.

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:

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(a) rate =- d[A]

dt= k [A] (eq. 4)

(b) rate =- d[B]

dt= k [B]

2(eq. 5)

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 mathematicaltransformations of these equations can be found in an introductory calculus

textbook.(a) ln[A] = -kt + ln[A]o (eq. 6)

(b)

1

[B]= kt +

1

[B]o(eq. 7)

([X]o= initial concentration of X)

Two things are apparent from these transformed equations. The first is thatthey relate the actual concentration of the species to the time that has elapsedsince the reaction began. The second is that the form of the final integratedequation depends on the initial rate law. A third thing, which is not soimmediately 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 usuallygiven 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 issimple first order, a graph of the natural log of concentration vs. time will be astraight line. If a reaction is simple second order, a graph of the reciprocal ofconcentration vs. time will be a straight line. This provides a very powerful yetsimple method to determine the order of a reaction. One merely measures theconcentration of the reactant as a function of time and graphs the log (or thereciprocal) vs. time to see if it is first or second order. (There are other ways ofdetermining order this is just one method.) In this experiment, you will measurethe concentration of a reactant at various times and graphically determine the or-der using these principles.

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

Chemical reactions always proceed more rapidly at higher temperatures unlessthe mechanism of the reaction changes as the temperature increases. (Somebiochemical reactions go more slowly at elevated temperatures, but this isbecause the mechanism of the reaction is affected by the increased temperature.)The famous Swedish chemist, Svante Arrhenius, studied the effect of temperatureon reaction rates in the late 1800s and discovered that the rate constant of areaction increased logarithmically in proportion to the reciprocal of the absolutetemperature (remember, we said earlier that temperature affected the rateconstant). 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 relatedto the activation energy for the reaction by C = Ea/R (Ea= activation energy and

R = the gas law constant). This makes eq. 8 into:- 4 -


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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 (k1at T1and k2at

T2), then the activation energy can be determined using eq. 9 twice (the first is

subtracted from the second) as:

lnk2k1

=Ea

R

1

T1

1

T2

(eq. 10)

In eq. 10, since the two rate constants and the two temperatures are known (havebeen measured), and R is a universal constant, the only unknown is the activationenergy. In this experiment, you will determine rate constants at two differenttemperatures and use eq. 10 to determine the activation energy for the reaction.

Part E: The Actual Reaction Studied______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________

Todays reaction is the hydrolysis (reaction with water)of tertiary-butyl bromide(I). This molecule reacts as shown below to form the products tertiary-butylalcohol (II) and HBr.

H3C H3C

H3C- C|

|-Br + H2O H3C- C

|

|-OH + HBr (eq. 11)

H3C H3C

(I) (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 thesame as the rate of disappearance of tBB. When measuring the rate at which HBrforms, 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).______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________

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 bottle6. 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 willdissolve - it is not soluble in water alone) into the 250 mL Erlenmeyer flask andadd 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, rinseand fill your burette with the 0.20 N NaOH solution. It will be advantageous tohave the initial reading be 0.00 mL. [Dont forget to eliminate the air bubblesfrom the tip before taking the initial reading.]

When the solvent has completely chilled and you have recorded an initial

reading (0.00 mL), run about2 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 yourflask (it should be pink at this time). Record the exact timewhen the tBB isinjected into your flask. Gently swirl the flask to mix the contents and allow theflask to sit in the ice bath and observe the color. Swirl the flask from time to timeto keep it thoroughly mixed. Record the exact timewhen the flask changes frompink to colorless. Then, without changing anything else, add another 2 mLportion from the burette (the solution should become pink again) and record theburette reading. Again watch the flask and record the exact timewhen the flaskbecomes colorless. Repeat this process until you have made a total of 7 additionsof NaOH. For the last 3 additions, you may add 1.5 mL of NaOH rather than 2mL.

The only data that you need to record during this time are (1) the actual burettereadings, and (2) the actual clock timeswhen the solution becomes colorless. Youdo not need to record the time when the NaOH is added from the burette.

After the solution has become colorless after the 7 thaddition of NaOH, remove

the flask from the ice bath. Fill a large beaker about 1/4full with tap water and setup 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 mayuse tap water running over the bottom of the flask). Place the flask under theburette 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, notjust the amount added after heating the flask!

Do the entire experiment a second time, this time eliminating the ice bath. Thereaction 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 #1since you want to continue addition to #1 from the point where you stoppedbefore heating it.) After taking your last time reading, put this flask in the waterbath, cool, and titrate to a final endpoint as you did with #1.

Part G: Calculations______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________

To understand the calculations, we first must understand that the rate of thisreaction depends in some way on the amount of tBB still remaining in the flaskatany particular time, rather than the amount that has reacted. We must be able touse the information we have collected to produce numbers that vary in the samefashion 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 waspresent 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 isthe 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 amountof tBB that has reactedat each point (when the solution becomes colorless). Thuswe can get a measure of how much tBB still remains in the flaskby calculatinghow 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 onthe concentrationof reactant, rather than just on the amount present. As we addbase during the reaction, the volume changes, so we need to calculate the newvolume at each point along the way. If Vorepresents 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 (Vo + bt). Since concentration isamount/volume, we can divide these two expressions to get the tBB concentrationat any time. (This doesnt give the true concentration, but gives a number thatbehaves exactly like the concentration, thus it can be treated graphically.)

In summary, the expressions below are used in calculations:

Symbol Represents

b total amount of tBB injected into flask (a constant)

bt total amount of tBB that has reacted at time = t

(b bt) total amount of tBB remaining in flask at time = t

Vo initial volume of solution (100 mL in this case)

(Vo+ bt) total volume of solution at time = t

(b bt) / (Vo+ bt) 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 thelist above - namely the concentration of tBB at time = t. The rate of the reactiondepends on this number in some way (the reaction is either simple first order or secondorder). 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.timeand the other of vs. time(see discussion on page 2 and 3). The graph that is thestraight linetells us the order of the reaction. Once we find the correct graph (andorder), 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. timeand 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 twotemperatures. Use this data in eq. 10 to calculate the activation energy for thereaction. Use the value of R listed by eq. 9, remembering to use absolute orKelvin temperature.

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Name____________________ Partner__________________ Lab Date_________ Date Submitted__________

Reaction Kinetics: The Rate of Hydrolysis of Tertiary-ButylBromide

Raw Data - Cold Raw Data - Room Temperaturetemperature of solution in ice bath: temperature of solution:

burette reading(mL)

clock readingwhen colorless

total elapsedtime (sec.)

burette reading(mL)

clock readingwhen colorless

total elapsedtime (sec.)

0.00 (injection) 0.0 0.00 (injection) 0.0

final volume - - - - - final volume - - - - -

ANALYSIS OF DATA H =

Coldtemp. of solution in ice bath: C ( K)

b(infinity reading): mL

elapsedtime (t)

base added(bt)

(b bt) (Vo+ bt) H ln H

0 0.00 100

infinity

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Room Temperature

temp. of solution : C ( K)

b(infinity reading): mL

elapsedtime (t)

base added(bt) (b bt) (Vo+ bt) H ln H

0 0.00 100

infinity

k1= ________k2= ________order = _____Eact= ____________

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Instructors Notes

Stockroom Needs______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________

1. Chemicals:

50/50 isopropanol/water mixture (by volume) - Each pair of students will needabout 300 mL total of this, part of which is in the form of an NaOH solutiondescribed 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 25-30students. About 2/3of the solution should be water-isopropanol solvent. Theseliquids tend to mix slowly when combined, so the mixture will need to bethoroughly agitated for a good while after the water and isopropanol arecombined. [Drug store rubbing alcohol is 70% isopropyl alcohol and water. Bymixing 300 mL of water with 700 mL of rubbing alcohol, the suitable solventmay be made. Although the author sees no apparent problem, he has not testedthe experiment in this less expensive manner. Please report your results if youshould attempt it.]

0.2 N NaOH solution in 50/50 water/isopropanol solvent - About 1/3of the abovesolvent 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 nochange in solvent characteristics takes place when base is added to the flaskduring 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 2-bromo-2-methylpropane or 2-methyl-2-bromopropane; Sigma-Aldrich ChemicalCo, 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 labof about 26 students will use about 15 grams of this (it is dispensed by theinstructor with syringes or marked Beral pipettes, so not much waste occurs).

Each kinetic run requires an injection of 0.5 cm3of tBB and each pair of studentsdoes 2 runs.

2. Apparatus:

50 mL burettes - It would be good if there were one burette per student (two perpair), or about 26 burettes per lab - maybe a few extra so leaking burettes can bereplaced. 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 110 C thermometers - Oneper 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 fordispensing the tBB. Since the tBB chews up the plastic a bit, they cannot bereused 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 alittle more.

References______________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________________

Shakhashiri, Bassam Z., Chemical Demonstrations, Volume 4,10.7 Hydrolysis of 2-

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

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O

O

O

O

O

O

O

O

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0 100 200 300 400 500 6

[

concentration]

time (sec.)

concentrationvs. time@ 297K

R2 ! 0.886

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O

OO

O

O

O

O

"4.5

"4

"3.5

"3

"2.5

"2

"1.5

0 100 200 300 400 500

#n

(concentratio

n)

time (sec.)

#n (concentration)vs. time@ 297K

$(%) ! "0.004370&% "1.840

R2 ! 0.9998

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O O O

O O

O

O

0

10

20

30

40

50

60

70

80

90

0 100 200 300 400 500

time (sec.)

vs. time@ 297K

R2 ! 0.8986

1

concentration

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O

O

O

O

O

O

O

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0 500 1000 1500 2000

time (sec.)

concentration

vs. time @ 276K

= 0.9585R2

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O

O

O

O

O

O

O

6

8

10

12

14

16

18

20

22

0 500 1000 1500 2000

time (sec.)

vs. time

@ 276K

1

concentration

= 0.9811R2

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O

O

O

O

O

O

O

O

"3.2

"2.7

"2.2

0 500 1000 1500 2000 250

time (sec.)

#n (concentration)

vs. time @ 276Kf(x) = -0.0005399*x -1.826

R2

= 0.9982

18

Fail Safe Kinetics Lab

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