Fractional Distillation of Esters

Fractional distillation is a technique used to separate mixtures of compounds into pure components. At a given temperature, a pure liquid has a specific vapor pressure. Heating the liquid provides a greater mole fraction of molecules with the kinetic energy needed to escape into the gas phase. This temperature, when the vapor pressure of a liquid equals the atmospheric pressure, is defined as the boiling temperature of a substance. f substances in a mixture have significantly different vapor pressures, they can be separated by a technique known as simple distillation. n simple distillation, a mixture is warmed slowly and the most volatile liquid vapori!es first. The vapor is then condensed back to liquid and collected in a separate flask. For mixtures of compounds with similar boiling points, you could perform a simple distillation multiple times, or employ fractional distillation. A fractionating column is one designed to allow multiple simple distillations to occur over its length "see Figure #$. %ne type of fractionating column is a long glass tube packed with glass or ceramic beads which allows the vapor to condense and vapori!e multiple times as it travels up the column. &ach cycle of condensation and evaporation is called a theoretical plate. The more theoretical plates in the column, the better the separation between the compounds in a mixture will be.

Figure 1 Fractional distillation apparatus

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Figure ' is a graphical representation of the temperature of the distilling vapor as a function of the volume of distillate in a two(component mixture. The black curve represents a practically ideal distillation in which the lower boiling component distills completely "the volume of collected fraction increases as the temperature stays constant$ and then the higher boiling component distills. The gray curve is an example of what actually occurs in many distillation processes) the first distillate is enriched in the lower boiling component and the final distillate is enriched in the higher boiling component. *y carefully controlling the temperature and by using a column with an optimum surface area for your mixture, it is possible to conduct a fractional distillation that will make the empirical curve "gray$ closely follow the ideal curve "black$, thus achieving the best possible separation of the mixture+s components.

Figure 2 Distillation of a mixture of two substances Fractional distillation is a slightly more complex process than it may seem, considering that you are simply slowly heating a mixture of two liquids so the liquid with the lower boiling point will vapori!e first. t will be important for your understanding of this distillation technique to read about theoretical plates as they relate to fractional distillation, as well as study ,c-abe(Thiele diagrams describing this process.

OBJECTIVES
n this experiment, you will

,easure and analy!e the retention times and peak areas of ethyl acetate and butyl acetate. -onduct the fractional distillation of a mixture of ethyl acetate and butyl acetate. ,easure and analy!e the retention times and peak areas of the fractions. &stimate the mole fraction of the components of the mixture.

MATERIALS
.ab/uest or computer .ab/uest App or .ogger Pro 1ernier ,ini 2fractional distillation apparatus # . glass syringe Temperature 5robe 6imwipes7 or paper towels heating mantle or oil bath vials of0 ethyl acetate butyl acetate 34034 ethyl acetate and butyl acetate acetone five #4 m. graduated cylinders boiling stone 5arafilm7

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Fractional Distillation of Esters

PRE-LAB EXERCISE
#. 8hat are the boiling points of ethyl acetate and butyl acetate9 '. :raw the molecular structures of these compounds.

PROCEDURE
Part I Con !ct t"e Fractional Distillation of a Mi#t!re of Et"$l Acetate an B!t$l Acetate

#. %btain and wear goggles. 5rotect your arms and hands by wearing a long(sleeve lab coat and gloves. -onduct this reaction in a fume hood or a well(ventilated room. '. ;et up the fractional distillation apparatus for your experiment, as shown in Figure #. <se #4 m. graduated cylinders to collect the distillates. =. %btain '4 m. of the unknown ethyl acetate>butyl acetate mixture and transfer it to the round( bottom flask. Add a boiling stone to the flask, and reattach it to the apparatus. CAUTION0 Ethyl acetate and butyl acetate are both hazardous in case of ingestion or inhalation. ?. 8arm the flask until distillate begins to collect in your graduated cylinder. @ecord the temperature of the vapor when the first drop of distillate is collected in your graduated cylinder. f this temperature is significantly below the boiling temperature of ethyl acetate, or more than 3- above the boiling temperature of ethyl acetate, you may have an improperly placed thermometer. 3. f necessary, adAust the heat so the collection rate of the distillate is about # drop per second.

B. Cou will collect five fractions, using a separate graduated cylinder for each fraction. -ollect the fractions according to the chart below. For the 'ndD3th fractions, you need not collect an exact volume. After you collect each fraction, seal the graduated cylinder with a square of 5arafilm. Important0 :o not allow the round(bottom distilling flask to go dry.
1st fraction Temperature range (C) "o#ume (drops or m$) 768 51 drops 2nd fraction 8 84 %2 m$ 3rd fraction 8488 %3 m$ 4th fraction 8812 %3 m$ 5th fraction !12 %3 m$

Part II Anal$%e t"e Fractions &$ 'as C"ro(ato)ra*"$

E. %btain a glass syringe and four vials containing acetone, ethyl acetate, butyl acetate, and a mixture of ethyl acetate and butyl acetate. The acetone will be used only to clean the syringe. CAUTION0 Ethyl acetate and butyl acetate are both hazardous in case of ingestion or inhalation. F. 5repare the 1ernier ,ini 2- for data collection. a. Turn on the ,ini 2-. b. -onnect the ,ini 2- to the <;* port on your computer or .ab/uest. c. ;tart the data collection program, and then choose Gew from the File menu.

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d. To bring up the Temperature(5ressure profile, tap H in .ab/uest or click -ollect in .ogger Pro. e. ;et the Temperature(5ressure values to0
&tart temperature 'o#d time (amp rate *ina# temperature 'o#d time Tota# #ength ,ressure 4 C 1 min 1 C)min 65C 3 min 6+5 min 5+ -,a

f. ;elect :one to initiate the ,ini 2- warm up. 8hen the ,ini 2- is ready for inAection in ;tep #', the message will read, I nAect and select -ollect simultaneouslyJ, and the .&: will turn to green. -ontinue with ;tep K during warm up. K. Follow the steps below to clean and flush the syringe with acetone. Important0 The glass syringe is fragile. *e careful not to bend the needle or bend the plunger. Gever pull the plunger back more than 34L of its total volume. *e careful not to bend the plunger as you press it down. a. :epress the plunger fully. b. ;ubmerge the tip of the syringe needle into the vial of acetone. c. 5ull back the plunger to fill the barrel about #>= full of acetone. &xamine the barrel of the syringe and estimate the amount of acetone in the barrel. d. &xpel the liquid onto a 6imwipe or a paper towel. e. @epeat steps aDd at least two times, until you are comfortable pulling up a liquid into the syringe and measuring the volume in the syringe barrel. <se a 6imwipe or a paper towel to carefully pat around the tip of the syringe needle. #4. Follow the process in ;tep K to clean and flush the syringe with ethyl acetate, the first sample to be inAected into the ,ini 2-. ##. -ollect a volume of ethyl acetate for inAection. a. ;ubmerge the tip of the needle into the vial of ethyl acetate one last time. b. :raw up 4.#4 . of liquid. Note0 t is important that the volume be exactly 4.#4 .. c. After collecting your sample, gently wipe the needle from barrel to tip, with a 6imwipe.

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Fractional Distillation of Esters #'. 5repare for inAection and the start of data collection. a. The ,ini 2- should now have reached the correct start temperature and pressure, and the .&: turned to green. b. To insert the needle of the syringe into the inAection port of the ,ini 2-, hold the syringe with one hand and steady the needle with your other hand, as shown in Figure =. nsert the needle into the inAection port until the needle stop is fully seated. f the needle sticks, rotate it slightly while inserting. :o not move the plunger yet. c. ;imultaneously, depress the syringe plunger and select -ollect to begin data collection. 5ull the needle out of the inAection port immediately. #=. 8hile the data collection proceeds, repeat ;tep K to thoroughly clean the syringe and needle. t may take more than three flushes to feel the syringe plunger move smoothly again, which is your indicator that the syringe and needle are both suitably clean. #?. The data collection will end after B.3 minutes. %bserve the graphed data that characteri!e an ethyl acetate chromatogram. #3. Analy!e your chromatogram. a. -hoose 5eak ntegration from the Analy!e menu. b. ;elect the left(most peak. To do this, drag from a little before the peak to a point far enough to the right that includes the entire peak. -hoose Add. c. @ecord the retention time and the peak area in your data table. d. -lick -ancel to return to the graph. #B. .abel and store your run of data0 n .ab/uest App, tap the Table tab. Highlight the heading, @un #, with your stylus, and replace it with the name of your compound. Tap on the 2raph tab to return to the graph. Tap the File -abinet icon to store the run. n .ogger Pro, double(click .atest, which is the title of your run of data in the table, to the left of the graph. n the :ata ;et %ptions dialog box, type in the name of your compound. -lick %6. -hoose ;tore .atest @un from the &xperiment menu to store your chromatogram.

Figure 3

#E.

5repare the butyl acetate sample. a. -lick -ollect in .ogger Pro, or tap . in .ab/uest, to bring up the Temperature(5ressure profile. This profile will be the same as for your previous run. f you are satisfied with these values, click :one. b. 8hile the ,ini 2- adAusts to its Temperature(5ressure profile, repeat ;teps #4 and ## with the butyl acetate sample. c. After the ,ini 2- is ready, repeat ;teps #'D#B.

#F. @epeat ;tep #E for the ethyl acetate>butyl acetate mixture and the five fractions you collected from the fractional distillation in 5art .

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#K. After you have completed the test of the mixture, save your file for use at a later time. ;ave the file on a <;* flash drive, computer, or .ab/uest, as directed by your instructor. '4. Flush and clean the syringe with acetone. '#. Turn off the ,ini 2-. 6eep your test results open in .ogger Pro or the .ab/uest App) you will need to refer to the various chromatograms to answer the :ata Analysis questions.

DATA TABLE
Part I Res!lts Compound eth/# acetate (0t12c) 3ut/# acetate (4u12c) 0t12c)4u12c 5i6ture (etention time (min) ,ea- area

Part II Res!lts *raction 1 2 3 4 5 Temperature range (C) "o#ume co##ected (drops or m$)

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Fractional Distillation of Esters

Anal$sis of t"e C"ro(ato)ra(s ,ea- area 0t12c 2cetate mi6ture 1st *raction 2nd *raction 3rd *raction 4th *raction 5th fraction ,ea- area 4u12c 2rea 0t12c7 2rea 4u12c

DATA A+AL,SIS
#. *ased on the distillation and 2- data, what was the ethyl acetate0butyl acetate ratio for each fraction 9 '. How well did your fractionating column separate the chemicals9 8hat could you change to achieve better separation9 =. 8hat is the estimated mole fraction for each ester in your known mixture9 The mixture was prepared using equal volumes of ethyl acetate and butyl acetate. The density of ethyl acetate is 4.FEK g>m. and the density of butyl acetate is 4.F44 g>m..

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I+STRUCTOR I+FORMATIO+
#. 8e recommend having vials of each compound available to the student, with back(up vials retained by the instructor. f a student contaminates a vial by mistake or spills a compound, the back(up vials can be used as replacements. '. 8e strongly recommend using reagent grade compounds for the best, most reliable results. =. 1ials must be kept tightly sealed when not in use. These compounds are highly volatile and will evaporate quickly. ?. All of these compounds should be used in a well(ventilated area. *e familiar with the ,;:; information for each compound and follow safe handling practices. 3. ;electing the peak region is a skill that requires practice and guidance from you. Cour students will need help Audging how much of the chromatogram to capture for a peak. Cou can be generous if you have only one peak to analy!e. 8ith multiple peaks, students need to be consistent in how they select a region. B. *ecause of the manner in which the ,ini 2- operates, the retention time is the MDvalue at the maximum CDvalue "in millivolts, m1$ of the peak. E. This experiment may be done using simple distillation, because the boiling temperatures of ethyl acetate "EEN-$ and butyl acetate "#'BN-$ are significantly different. t may be interesting to have groups of students use either simple or fractional distillation and compare results.

-A.ARD ALERTS
5ropyl acetate0 Highly flammable liquid and vapor. ,ay be harmful if inhaled. -auses respiratory tract irritation. 1apours may cause drowsiness and di!!iness. ,ay be harmful if absorbed through skin. -auses skin irritation. @epeated exposure may cause skin dryness or cracking. -auses eye irritation. ,ay be harmful if swallowed. H, ; -lassification0 Health ha!ard', Flammability=, 5hysical ha!ard4. *utyl acetate0 Flammable liquid and vapor. ,ay be harmful if inhaled. -auses respiratory tract irritation. 1apors may cause drowsiness and di!!iness. ,ay be harmful if absorbed through skin. -auses skin irritation. @epeated exposure may cause skin dryness or cracking. -auses eye irritation. ,ay be harmful if swallowed. H, ; -lassification0 Health ha!ard', Flammability=, 5hysical ha!ard4. Acetone0 Fire ha!ard "flash point #E.4N-$. ;tore in dedicated flammables cabinet. ,oderately toxic by inhalation or ingestion. ,oderately toxic by ingestion. 1apor causes weakness, fatigue, nausea and headache. ;kin and eye irritant. H, ; -lassification0 Health ha!ard', Flammability=, 5hysical ha!ard4. The ha!ard information reference is ;igma(Aldrich -o., #(F44(='3(=4#4, www.sigmaaldrich.com>safety(center>msds(search.html.

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Fractional Distillation of Esters

SAMPLE C-ROMATO'RAMS

First fraction

Third fraction

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Fifth fraction

10

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