Fractional Distillation

Fractional Distillation

Fractional Distillation is a technique used to separate mixtures of compounds when the compounds have similar boiling points. At a given temperature a pure liquid has a specific vapor pressure. Heating the liquid provides more and more molecules with the energy required to escape into the gas phase. The temperature at which the vapor pressure of a liquid equals the atmospheric pressure is defined as the boiling point.

If two compounds have vastly different vapor pressures, they can be separated by a technique known as simple distillation. In a simple distillation, a mixture is warmed so that the more volatile liquid vaporizes first. The vapor is collected in a separate flask for condensation back to liquid. For mixtures of compounds with similar boiling points, one would need to perform a simple distillation multiple times, or conduct a fractional distillation.

A fractionating column is one designed to allow multiple simple distillations to occur over its length (see Figure 1). A long glass tube is packed with glass or a ceramic material which allows the vapor to condense and vaporize multiple times as it travels up the column. Each cycle of condensation and evaporation is called a theoretical plate. The more theoretical plates available in the column, the more precise the separation achieved between two compounds in a mixture.

Figure 1 Distillation column

For a very efficient distillation, the temperature vs. volume distillate graph might look like the one shown below.

Figure 2 Temperature vs. volume distillate graph

At any given temperature for a distillation the lower boiling component of a mixture makes a larger contribution to the vapor composition than the higher boiling component. In the example below, A has a lower boiling point. The vapor is richer in A than the liquid from which it escaped.The two points (“y” and “x”) give the two concentrations which are in equilibrium.

Figure 3 Boiling point diagram for a mixture of two liquids

OBJECTIVES

In this experiment, you will

Measure and analyze the retention time of ethyl acetate and butyl acetate as they pass through a Vernier Mini GC.

Conduct the fractional distillation of a mixture of ethyl acetate and butyl acetate.

Measure and analyze the retention time of the fractions.
Calculate the percent composition of each substance in the mixture.

MATERIALS

Vernier Mini GC / vials of:
computer or LabQuest / ethyl acetate
Logger Pro 3 or LabQuest App / butyl acetate
fractional distillation apparatus / 50:50 ethyl acetate and butyl acetate
1 L glass syringe / acetone
Temperature Probe / boiling stones
Kimwipes®or paper towels / Parafilm®
heating mantle or oil bath / three 25 mL graduated cylinders

PRE-LAB EXERCISE

1.What are the normal boiling points of ethyl acetate and butyl acetate?

2.Draw the structural formulas of these compounds.

PROCEDURE

Part I Conduct the Fractional Distillation of a Mixture of Ethyl Acetate and Butyl Acetate

1.Obtain and wear goggles.

2.Set up the fractional distillation apparatus for your experiment. Use 25 mL graduated cylinders to collect the distillates.

3.Obtain 20 mL of the ethyl acetate/butyl acetatemixture and transfer it to a round-bottom flask. Add a boiling stone to the flask.CAUTION: Ethyl acetate and butyl acetateare both hazardous in case of ingestion or inhalation.

4.Warm the flask until distillate begins to collect in your graduated cylinder. Record the temperature of the vapor when the first drop of distillate is collected in yourgraduated cylinder. Consult your instructor if this temperature is (a) below the b.p. ofethyl acetate, or
(b) more than 5C above the b.p. of ethyl acetate. You may have animproperly positioned thermometer.

5.If necessary, adjust the heat so the collection rate of the distillate is about 1 drop per second.

6.Record the temperature after each mL of distillate is collected. Set up your own chart or table to keep a record of the temperature during the distillation process.

7.You will collect three fractions, using a separate graduated cylinder for each fraction.Important: Do not allow the round-bottom distilling flask to evaporate to dryness.

First fraction: from the first drop until the temperature has risen past 83C, or you see a rapid decrease in temperature. Record the volume. Use a square of Parafilm to tightly seal the graduated cylinder to prevent evaporation.
Second fraction: until the temperature rises to 5C below the literature value b.p. of
butyl acetate. Record the volume and seal the graduated cylinder with a square of Parafilm.
Third fraction: until a total of all three fractions is 16 mL. Record the volume of the
3rd fraction and seal the graduated cylinder with a square of Parafilm.

Part II Analyze the Fractions by Gas Chromatography

8.Obtain a glass syringe and three vials containing: ethyl acetate, butyl acetate, and a mixture of ethyl acetate and butyl acetate. CAUTION: Ethyl acetate and butyl acetate are both hazardous in case of ingestion or inhalation.

Important: The glass syringe is fragile and can be easily damaged. Be careful not to bend the needle or bend the plunger. If the plunger is accidentally pulled out of the glass barrel, reinserting it is extremely difficult, sometimes impossible.

9.Prepare the Vernier Mini GC for data collection.

Turn on the Mini GC.
ConnecttheUSB cable of the Mini GC to the USB port on your computer or LabQuest.
Start the data-collection program, and then choose New from the File menu.
Click Collect in Logger Pro, or tap►in LabQuest, to bring up the Temperature-Pressureprofile.
Set the Temperature-Pressure values to:

Start temperature / 35C
Hold time / 1 min
Ramp rate / 10C/min
Final temperature / 65C
Hold time / 2 min
Total length / 6.0 min
Pressure / 7.0 kPa

Select Done to initiate the Mini GC warm up. Note: A new message will appear, “Do not inject until GC is ready”, and the LED on the Mini GC is red. The Mini GC will take a few minutes to warm up and stabilize. When the Mini GC is ready for injection in Step 13, the message will read, “Inject and select Collect simultaneously” and the LED will turn to green. Continue with Step 10 during warm up.

10.Follow the steps below to clean and flush the syringe with acetone.Important: The glass syringe is fragile. Be careful not to bend the needle or bend the plunger. Never pull the plunger back more than 50% of its total volume. Be careful not to bend the plunger as you press it down.

Depress the plunger fully.
Submerge the tip of the syringe needle into the vial of acetone.
Pull back the plunger to fill the barrel about 1/3 full of acetone. Examine the barrel of the syringe and estimate the amount of acetone in the barrel.
Expel the liquid onto a Kimwipe or a paper towel.
Repeat Steps a–d at least two times, until you are comfortable pulling up a liquid into the syringe and measuring the volume in the syringe barrel. Use a Kimwipe or a paper towel to carefully pat around the tip of the syringe needle.

11.Follow the process in Step 4 to clean and flush the syringe with ethyl acetate, the first sample to be injected into the Mini GC.

12.Collect a volume of ethyl acetate for injection.

Submerge the needle into the vial of ethyl acetate one last time.
Draw up approximately 0.2 L of liquid. It is not critical that the volume be exactly 0.2L; a tiny bit more or less volume is all right.
After collecting your sample, gently wipe the needle from barrel to tip, with a Kimwipe.

13.Prepare for injection and the start of data collection. It is important for you and your lab partner to divide the tasks in this step. One person will operate the syringe and the other person will operate the computer controls.

When the Mini GC has reached the correct start temperature and pressure, the message reads, “Ready to Inject,” and the LED on the Mini GC is green.
To insert the needle of the syringe into the injection port of the Mini GC, hold the syringe with one hand and steady the needle with your other hand.Insert the needle into the injection port until the needle stop is fully seated, as shown in Figure 5. If the needle sticks, rotate it slightly while inserting. Do not move the plunger yet.
Simultaneously, depress the syringe plunger andselectCollect to begin data collection. Pull the needle out of the injection port immediately.

14.While the data collection proceeds, repeat Step 10 to thoroughly clean the syringe and needle. It 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.

15.Data collection will end after 6 minutes. Observe the graphed data that characterize an ethyl acetate chromatogram.

16.Analyze your chromatogram.

Choose Peak Integration from the Analyze menu.
Select and integrate the left-most peak. To do this, drag from a little before the peak to a point far enough to the right that includes all of the peak. Then choose Add.
Record the retention time and the peak area in your data table.
Enter the name of the compound, if known.
To analyze another peak on the same graph, repeat Steps b and c.
When you are finished with all of the peaks, select OK.

17.Complete one or both of the following as directed by your instructor.

Print your chromatogram.
You can choose to save this chromatogram and peak analysisfor later use, with a unique file name, by choosing Save from the File menu.

18.Prepare the butyl acetatesample.

Click Collect in Logger Pro, or tap►in LabQuest, to bring up the Temperature-Pressure profile. This profile will be the same as for your previous run. If you are satisfied with these values, click OK to initiate the Mini GC profile.
While the Mini GC adjusts to its Temperature-Pressure profile, repeat Steps 11 and 12 with the 1-butanol sample.
After the Mini GC is ready, repeat Steps 13–18.

19.Repeat Step 18 for the ethyl acetate/butyl acetatemixture and the three fractions you collected from the fractional distillation in Part I.Note: Make sure to record the % ethyl acetate and % butyl acetatefor the mixture and the three fractions you collected from the distillation.

20.When you have completed your final data-collection run, turn off the MiniGC.

DATA TABLE

Part I Results

Compound / Retention time (min) / Peak area
ethyl acetate (EtOAc)
butyl acetate (BuOAc)
EtOAc/BuOAc Mixture

Part II Results

Fraction / Temperature range / Volume collected
1
2
3

Analysis of the Chromatograms

Peak area EtOAc / %EtOAc / Peak area BuOAc / %BuOAc
EtOAc/BuOAcmixture
1stfraction
2ndfraction
3rdfraction

DATA ANALYSIS

1.Based on the distillation and GC data, what percent of each substance was in your mixture? Explain.

2.How well did your fractionating column separate the chemicals? What could you change to achieve better separation?

3.Why does a rapid distillation that floods the column lead to poor separation of components?

4.What would happen to the separation of chemicals in the GC if the temperature was started out at 90C?

5.What is the mole fraction for each ester in your known mixture? The mixture was prepared using equal volumes of ethyl acetate and butyl acetate. The density of ethyl acetate is
0.879 g/mL and the density of butyl acetate is 0.800 g/mL.

Gas Chromatography Investigations4-1