5.

Distillation and Boiling Points

Read the introduction and the appropriate experiments below. You will be doing either Procedure 1A or 1B or 2A or 2B (see desk assignment below.) In your lab notebook using carbon copies, you are ONLY required to write the PRELAB section for the experiments that you will actually be running in the laboratory. Your experiment assignment can be determined according to the following diagram:
End desks closest to the window will do Exp't 1A Inside desks closest to the hall will do 2A

Windows

1A

Hood

2B

2A

Hood

1B

Inside desks closest to the window will do Exp't 2B

End desks closest to the hall will do 1B

All students will do Procedure 3, microscale fractional distillation of mixture of two unknown liquids. You will share your data from Procedures 1 or 2 with the three other students on your side of the lab bench. You will then be able to compare the efficiency of simple versus fractional distillation for two different systems: toluene/cyclohexane and ethanol/water. In your lab notebook, using carbonless copies, write an introductory PRELAB section for the distillation experiment including: 1. A brief Summary of what will be done and why it will be done for the experiments below. 2. Three Learning Objectives or Goals for the experiment. 3. Diagrams of Apparatus. There are no chemical reactions in this experiment. 4. Chemical Data Tables Complete the rest of your Common Shelf Chemical Data Table and turn in a photocopy of it with your PreLab. You should look up the chemicals not on the Chemical Shelf Chemical Data Table (acetone, 1-butanol, 2-methyl-2-propanol (t-butyl alcohol) and enter them into a blank Chemical Data Table from the back of your notebook. 5. PreLab Exercise A mixture of 10 mL of isoamyl acetate (MW=130.2 g/mol and density=0.88 g/mL) and 15 mL of methyl benzoate (MW=136.2 g/mol and density=1.09 g/mL) is distilled. Calculate the mole percent for each component. Use these mole %s and the figure below to answer the following questions. 1. What is the initial boiling point of this liquid mixture? 2. What is the composition of the vapor in equilibrium with the liquid? What is the composition of the initial condensate from simple distillation? 3. If the same mixture were fractionally distilled, how would the composition of the first liquid collected be different from the initial condensate disucssed in question 2 above?
200 190 200 190

Hall
Sharing data PreLab Exercise The point breakdowns can be found on the grading sheet in Appendix A.4.

1A

Hood

2B

2A

Hood

1B

180 Temp o C 170

Vapor

180 170 Liquid 160

160

150 140 Mole % Isoamyl Acetate Mole % Methyl Benzoate 100 0 75 25 50 50 25 75 0 100

150 140

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Introduction
Distillation is an excellent method for purifying a liquid. A liquid contains closely packed but mobile atoms or molecules of varying energy. When a molecule of the liquid approaches the vapor-liquid phase boundary, it may, if it possesses sufficient energy, pass from the liquid phase into the gas phase. Only molecules energetic enough to overcome the forces which hold them in the liquid phase can escape into the vapor phase. Some of the molecules present in the vapor phase above the liquid may, as they approach the surface of the liquid, enter the liquid phase and thus become part of the condensed phase. In so doing, the molecules relinquish some of their kinetic energy (i.e. their motion is slowed). Heating the liquid causes more molecules to enter the vapor phase; cooling the vapor reverses this process. When the system is in equilibrium, as many molecules are escaping into the vapor from the liquid phase as are returning from the vapor to the liquid. The extent of this equilibrium is measured as the vapor pressure. If the system maintains equilibrium even when the energy is increased, more molecules in the liquid phase have energy sufficient to escape into the vapor phase. Although more molecules are also returning from the vapor phase, the number of molecules in the vapor phase increases and so does the vapor pressure. The exact number of molecules in the vapor phase depends mainly on the temperature, the pressure, and the strength of the intermolecular forces exerted in the liquid phase and the volume of the system. If two different components (designated A and B) are present in the liquid phase, the vapor above the liquid will contain some molecules of each component. The number of A molecules in the vapor phase will be determined by the vapor pressure of A and by the mole fraction of A in the mixture. In other words, the relative amounts of the components A and B in the vapor phase will be related to the vapor pressure of each pure liquid. This relationship is expressed mathematically as Raoults law:

Raoult's Law of Partial Pressures

Ptotal = PA + PB PA PB PA PB NA NB = = = = = =

where

PA = PANA and PB = PBNB

partial pressure of A partial pressure of B vapor pressure of pure A vapor pressure of pure B mole fraction of A in the liquid mole fraction of B in the liquid

The total vapor pressure above the liquid mixture is the sum of the two partial pressures of components A and B. As the temperature is raised, the vapor pressure of each component increases, thereby proportionately increasing the total vapor pressure above the liquid. At some temperature the sum of the partial pressures equals 760 torr (1 atm) and the solution begins to boil. More generally, the boiling point is defined as that temperature where the sum of partial pressures above the liquid equals the externally applied pressure on the system. Lowering the external pressure causes the solution to boil at a lower temperature - raising the external pressure causes the solution to boil at a higher temperature. Raoults law also provides information as to the composition of the vapor above a liquid:

XA = mole fraction of A in the vapor = PA/Ptotal XB = mole fraction of B in the vapor = PB/Ptotal

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Simple Distillation: Distillation occurs when a liquid is heated in a vessel and the vapors are passed through a condenser, allowing the vapors to convert back to a liquid (see Figure 5.1.) which flow into a different vessel from that used for the heating. A simple distillation is considered to be any distillation which does not involve a fractionating column or one in which an one liquid component is separated either from non-volatile substances or another liquid that differs in boiling point by at least 75. The condensate will have essentially the same mole ratio of liquids as the vapor boiling from the liquid. Simple distillation is not effective in separating closely boiling components of a mixture. Fractional Distillation: If a fractionating column is used in the distillation (see Figure 5.3)
it is possible to separate compounds with closer boiling points. The fractionating column is packed with some porous material (chore boy) which provides a large surface area for the multiple condensations and vaporizations to occur as the liquid ascends the column. Condensing of the higher-boiling vapor releases heat causing the vaporization of lower-boiling liquid on the packing so that the lower boiling component moves up while the higher boiling componenet moves down, some of it running back into the distilling flask. Each successive condensation/vaporization cycle affords a vapor that is richer in the more volatile fraction. As the temperature is raised the lower boiling fractions get enriched in the vapor. Consider a 60:40 mixture of cyclohexane (BP 81 C) and toluene (BP 110 C). This will boil at 88C. The vapor above this boiling mixture would consist of a 83:17 mixture of cyclohexane and toluene. The material then recondenses on the chore boy. The re-vaporization of this material at 83C produces a vapor with a 95:5 cyclohexane:toluene ratio. This process is depicted graphically in Figure 5.1 below. The lower curve represents the composition of the liquid and the upper curve the composition of the vapor corresponding to that liquid composition determined by drawing a horizontal line. A couple more cycles of condensation and vaporization will render the cyclohexane essentially pure. Each cycle is called a theoretical plate. The fractionating columns used in the organic labs have about 3 to 5 theoretical plates.

110

vapor composition curve

100 liquid-vapor temperature C 90

liquid composition curve

80 0 20 40 % Toluene 60 80 100

Figure 5.1: Liquid/Vapor Distillation Temperature-Composition Curves for Cyclohexane:Toluene mixtures

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Distillation Curves: If one plots the course of a simple and a fractional distillation (using
corrected thermometer readings), curves approximating those shown below in Figure 5.1 will result. These curves provide information as to the efficiency of the separation of components of a mixture. Another advantage of fractional distillation is that the flat portions (plateaus) of the graph of boiling point (Y axis) vs distillate volume (X axis) can be more easily distinguished than in a simple distillation. Therefore, the boiling points are more accurate and can be used to help identify the boiling fractions.

Simple and Fractional Distillation Curves

bp of pure B

Temperature ( C)

simple distillation

fractional distillation bp of pure A

Distillate Volume in mL or drops Figure 5.1: Simple vs. Fractional Distillation Data.

Azeotropes: Not all mixtures of liquids conform to Raoults law. For example, ethanol and
water, because of molecular interactions, form an azeotrope. A mixture of 95.5% ethanol and 4.5 % water boils below the boiling point of pure ethanol, and thus 100% ethanol cannot be prepared by distillation. A mixture of liquids of a certain definite composition that distills at a constant temperature without change in composition is called an azeotrope. The following experiments are designed to give you exposure to a number of different techniques using a variety of equipment including macroscale simple and fractional distillation, and microscale fractional distillation of an unknown two-component mixture to determine boiling points and thus identify the two liquids.

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Experimental Procedures
In any distillation the flask should not be more than two-thirds full at the start. Great care should be taken not to distill to dryness! There always exists the possibility that certain liquids, especially ethers, contain some explosive peroxides formed by exposure to air. These are higher boiling and can concentrate in the distilling flask as you distill. If you distill all the liquid from the flask, the temperature will rise very high, and this could cause the peroxides to explode violently.
DO NOT TRY TO TEAR "CHORE BOY" WITH YOUR HANDS! DEEP CUTS WILL RESULT! Use scissors from the Side-shelf. Occasionally the temperature scale on your thermometer may be inaccurate. It should be checked by measuring the known boiling and freezing points of a liquid such as water. All the people on one side of the bench can share one hot plate with boiling water bath to check the 100C point (corrected for atmospheric pressure, see next paragraph) and can also share one ice-water bath to measure the freezing point of water, 0C. If either is off by more than 1C, you should obtain another thermometer from the stockroom. Liquids boil lower if the atmospheric pressure is less than 760 Torr and higher if it is greater. To obtain a boiling point corrected to atmospheric pressure, add (or subtract) 0.5C to the observed boiling point for every 10 Torr the observed atmospheric pressure is below (or above) 760 Torr. For example, if your thermometer is accurate (see above) and reads 108C for the boiling point of toluene when the barometer reading is 720 Torr, the corrected boiling point of toluene would be about 110C (at 760 Torr). A barometer (with instructions for use) is available at the south end of Lab 215.
ring stands Checking the Thermometer.

Caution!

Correcting for Pressure Effects.

Simple Distillation

glass adapter for rubber thermometer adapter

rubber thermometer adapter

west condenser

100 mL flask with 1" stir bar in it heating mantle

3-way connecting tube

rubber band to hold adapter on

connecting tube water out magnetic stirrer Varistat Distillation Receiver: 10 mL graduated cylinder water in

Figure 5.2: Set-up for macroscale simple distillation.

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Procedures 1A and 1B
Assembling the Distillation Set-up for Simple Distillation.

Assemble the apparatus for simple distillation as shown in Figure 5.2. Start by placing your magnetic stirrer on the base of a ring stand and then attaching the electric heating mantle (without sand in it) to the ring stand so it rests on top of the stirrer. Plug the heating mantle into the Varistat, a variable voltage controller, on the side of the hood and plug the Varistat into the socket above your bench. Place a 1" stirring bar in a dry 100 mL round-bottomed flask from your blue kit and clamp this to the ring stand so that it fits snugly in the heating mantle. Stirring promotes even boiling and avoids bumping. As you assemble the apparatus, each ground joint is lightly greased by putting a very small dab of grease on the inner joint and spreading it over the surface of the joint. (Do not use excess grease as it will contaminate the product.) When pressed into the outer joint and twisted, the connection should appear almost transparent. Water enters the condenser at the connection nearest the distillation receiver. Because of the large heat capacity of water only a very slow flow is needed; too much water pressure will cause the tubing to pop off, causing a flood (and you will probably also get a shower). The condenser should be clamped to a separate ring stand. Rubber bands (Common Shelf) can be used to hold the angled connecting tube to the condenser. Collect the distilled liquid in a 10 mL graduated cylinder. This will have to be emptied into an Erlenmeyer flask a few times during the distillation. Be sure that the bulb of the dry thermometer is just below the opening into the side arm of the distillation head.

Procedure 1A
Caution!
Simple Distillation of a CyclohexaneToluene Mixture.

Caution: Cyclohexane and toluene are flammable; make sure distilling apparatus is vapor-tight. Remove the glass thermometer adapter and place a long-stem glass funnel in the 3-way connecting tube. Into this funnel, pour in a mixture of 25 mL of cyclohexane and 25 mL of toluene. Reassemble and after making sure all connections are tight, turn the magnetic stirrer on (lowest setting) and heat the flask strongly (Varistat setting = 70) until boiling starts. Then adjust the heat until the distillate drops at a regular rate of about one drop per second. Record temperature versus total volume of distillate at regular intervals, about every 2 mL. After 40 mL of distillate are collected, discontinue the distillation. Record the barometric pressure. Exchange data with the three other students on your side of a lab bench and record the distillation data so you have it for all four experiments: 1A, 1B, 2A, and 2B.

Cleaning Up

Cleaning Up Dispose of cyclohexane and toluene in the recycling containers provided. Do not pour them down the drain.

Procedure 1B
Simple Distillation of an Ethanol-Water Mixture.

Remove the glass thermometer adapter and place a long-stem glass funnel in the 3-way connecting tube. Into this funnel, pour 50 mL of 20% ethanol/80% water. Reassemble and after making sure all connections are tight, turn the magnetic stirrer on (lowest setting) and heat the flask strongly until boiling starts. Then adjust the heat until the distillate drops at a regular rate of about one drop per second. Record temperature versus total volume of distillate at regular intervals, every one or two mL. After about 25 mL of distillate are collected, discontinue the distillation. Record the barometric pressure, make any boiling point correction necessary, and plot boiling point versus volume of distillate. Exchange data with the three other students on your side of a lab bench and record the distillation data so you have it for all four experiments: 1A, 1B, 2A, and 2B.

Cleaning Up

Cleaning Up Dispose of distillate in the ethanol/water recycling containers provided. The distillation flask residue can be flushed down the drain.

66

Procedure 2A and 2B
Assemble the apparatus for fractional distillation as shown in Figure 5.3. Start by placing your magnetic stirrer on a ring stand and then attaching the electric heating mantle (without sand in it) to the ring stand so it rests on top of the stirrer. Plug the heating mantle into the variable voltage controller (Varistat), on the side of the hood and plug the varisatat into the socket above your bench. Place your 1" stirring bar in a dry 100 mL round-bottomed flask from your blue kit and clamp this to the ring stand so that it fits snugly in the heating mantle. Stirring promotes even boiling and avoids bumping. As you assemble the apparatus, each ground joint should be lightly greased by putting a very small dab of grease on the inner joint and spreading it over the surface of the joint. (Do not use excess grease as it will contaminate the product.) When pressed into the outer joint and twisted, the connection should appear transparent.
Assembling the Distillation Set-up for Fractional Distillation.

fractionating column wrapped with glass wool to prevent heat loss

rubber thermometer adapter

3-way connecting tube

glass adapter for rubber thermometer adapter

west condenser

distilling columnhalf full with metal helices steel wool pipet bulb 100 mL flask with 1" stir bar in it heating mantle

rubber band to hold adapter on water out

connecting tube Distillation Receiver: 10 mL graduated cylinder

ring stands

water in

magnetic stirrer Varistat Macroscale Fractional Distillzation Apparatus.

Figure 5.3: Set-up for macroscale fractional distillation

67

Caution! Do not try to tear Chore Boy with your hands! Deep cuts may result. If necessary, scissors are available at the stockroom.

The distilling column is packed by first pushing a wad of stainless steel sponge ("ChoreBoy") through from the larger end of the column until it rests against the three indents near the smaller end. Then stainless steel chips are added until the fractionating column is about one-third to onehalf full. The column should be perfectly vertical and one of the two water connections should be sealed with parafilm, a wad of tissue or a pipet bulb. To get higher boiling liquids through the fractionating column, you must insulate it and the boiling flask by wrapping it with glass wool. Water enters the condenser at the connection nearest the distillation receiver. Because of the large heat capacity of water only a very slow flow is needed; too much water pressure will cause the tubing to pop off, causing a flood. The condenser should be clamped to a separate ring stand. Rubber bands (Common Shelf) can be used to hold the bent connecting tube to the condenser. Collect the distilled liquid in a 10 mL graduated cylinder. This will have to be emptied into an Erlenmeyer flask a few times during the distillation. Be sure that the bulb of the thermometer is just below the opening into the side arm of the distillation head.

Procedure 2A
Caution!
Fractional Distillation of a CyclohexaneToluene Mixture.

Caution: Cyclohexane and toluene are flammable; make sure distilling apparatus is vapor-tight. Remove the glass thermometer adapter and place a long-stem glass funnel in the 3-way connecting tube. Into this funnel, slowly pour 25 mL of cyclohexane and 25 mL of toluene. Reassemble the apparatus and make sure all connections are tight. Turn on the magnetic stirrer to its lowest setting. Start heating the flask at a Varistat setting of 60 until the mixture of cyclohexane and toluene just begins to boil. As soon as boiling starts, turn down the power slightly. Heat slowly at first. A ring of condensate will rise slowly through the column. The rise should be very gradual so that the column can acquire a uniform temperature gradient. Do not apply more heat until you are sure that the ring of condensate has stopped rising; then increase the heat gradually. In a properly conducted operation, the vapor-condensate mixture reaches the top of the column only after several minutes. Once distillation has commenced, it should continue steadily, without any drop in temperature, at a rate not greater than 1 drop every 2 or 3 sec (2 mL in 1.5-2 min). Observe the flow and keep it steady by slight increases in heating as required. Record the temperature as each milliliter of distillate collects, and make more frequent readings when the temperature starts to rise abruptly. Record temperature versus total volume of distillate at regular intervals. Stop the distillation when a second constant temperature is reached. Record the barometric pressure and what you observed inside the column in the course of the fractionation. Exchange data with the three other students on your side of a lab bench and record the distillation data so you have it for all four procedures: 1A, 1B, 2A, and 2B. Cleaning Up Dispose of distilled and undistilled cyclohexane and toluene in the recycling containers provided. Do not pour them down the drain.

Cleaning Up

Procedure 2B
Fractional Distillation of an EthanolWater Mixture.

Remove the glass thermometer adapter and place a long-stem glass funnel in the 3-way connecting tube. Into this funnel, slowly pour approximately 50 mL of 20% ethanol/80% water. Reassemble and make sure all connections are tight. Turn the magnetic stirrer on to its lowest setting. Follow the procedure (Ex 2A above) for the fractional distillation of a cyclohexanetoluene mixture. After 25 mL of distillate are collected, discontinue the distillation. Record the barometric pressure and what you observed inside the column in the course of the fractionation. Exchange data with the three other students on your side of a lab bench and record the distillation data so you have it for all four procedures: 1A, 1B, 2A, and 2B. Cleaning Up Dispose of distillate in the ethanol/water recycling containers provided. The distillation flask residue can be flushed down the drain.

Cleaning Up

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Procedure 3
You will be supplied with an unknown that is a 50:50 mixture of two organic liquids selected from those listed in Table 5.1 below. (Record the unknown number immediately in your lab notebook.) Using microscale fractional distillation, you will determine their boiling points and this will allow the identification of the two liquid components of your unknown. The liquids in the mixture will be mutually soluble and differ in boiling point by more than 20C.
Microscale Distillation of an Unknown.

Solvent
Acetone Methanol Hexane 1-Butanol 2-Methyl-2propanol Water Toluene*

Boiling Point C
56.5 64.7 68.8 117.2 82.2 100.0 110.6

* Methanol and toluene form an azeotrope, bp 63.8C (69% methanol).

Table 5.1: Boiling Points of Possible Distillation Unknowns Set your magnetic stirrer on a ring stand and attach a heating mantle as you did in Ex 1 or 2 except fill your heating mantle half full with sand. Start heating it at a varistat setting of 50. To a 5-mL short-necked round-bottomed flask is added 4 mL of your distillation unknown and a halfinch (1/2 inch) magnetic stirring bar. Insert enough stainless steel Chore Boy into the distillation column to fill it LOOSELY (see Figure 5.4.) The thermometer bulb should be completely below the side arm of the distillation head so that the mercury reaches the same temperature as the vapor that distills. The thermometer will probably need to be clamped with the 3-prong micro-clamp so that it doesnt lean against the inside wall of the distillation head, which leads to erroneous temperature readings. The end of the distillation head dips well down into a 20 mL vial, which rests on the bottom of a 50 mL beaker filled with cold ice-water. The beaker is supported with a large clamp. Turn on the magnetic stirrer (lowest speed) and start the fractional distillation by piling hot sand up around the flask with a spatula to heat it. As soon as boiling starts, the vapors can be seen to rise up the neck of the flask. Adjust the rate of heating by piling up or scraping away sand from the flask bottom so that it takes several minutes for the vapor to rise to the thermometer: The rate of distillation should be no faster than three drops per minute. If your distillate vapors dont seem to be condensing into drops, wrap a 2" x 2" strip of wet paper towel around the distilling head side arm to cool it by evaporation.
Caution! Do not try to tear "Chore Boy" apart with your hands! Deep cuts often result! Use a pair of scissors if necessary.

69

distillation column wrapped with glass wool to prevent heat loss

20 mL vial

Distillation head

ice water in 50 mL beaker stainless steel wool

Distillation column

20 mL vial

control heating by moving hot sand toward or away from flask

Heating mantle half full with sand

Varistat

5 mL flask containing 1 cm stir bar

magnetic stirrer

Figure 5.4: Set-up for microscale fractional distillation of your unknown.

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Keep account of the total number of drops and record the temperature every few drops during the entire distillation. If the rate of distillation is as slow as it should be, there will be sufficient time between drops to read and record the temperature. Only collect fractions in separate vials if the boiling point data doesnt match one of the possible liquids in Table 5.1. In this case, you may need to do some other test. Stop the distillation as soon as you have enough data to determine the boiling point of the higher boiling component. Prepare a distillation curve of temperature versus number of drops (see Introduction above.) Identify the components from their boiling points. If the boiling points derived from your fractional distillation do not allow unambiguous identification of both unknown components, try a simple solubility test: hexane and toluene are the only completely water-insoluble liquids given as possibilities. Do not hesitate to ask your instructor for help. Cleaning Up Dispose of water-insoluble unknown distillates in the Nonhalogenated Organics Waste containers. Water-soluble unknown distillates (water, acetone, methanol) can be flushed down the drain. If necessary, test water solubility by squirting a few drops of water into the distillate. Carry your sandbath to the side shelf and dump the HOT! sand back into the sand supply bowl. Do NOT dump it in the waste bins. Glass wool may be reused over and over; return glass wool to the supply container.
Cleaning Up

Final Report
Record data and observations in your notebook as you work (see the section The Laboratory Notebook: OBSERVATIONS AND DATA section). For the RESULTS AND DISCUSSION section of your final lab report, follow the point distribution on the grading sheet for this experiment and be sure to include: (1) Four distillation curves of macroscale simple and fractional distillation data taken by you and the other students on your side of the bench. Make any atmospheric pressure boiling point corrections necessary, then plot boiling point versus volume of distillate (drops or mL) of the type shown in the curves in the Introduction. (2) The distillation curve for your unknown. (3) Give the identities of your two unknown liquids. (4) Discussion of simple versus fractional distillation. Do the results support predictions? PostLab Question: The liquid boiling in a simple distillation flask consists of 80 mole percent of hexane and 20 mole percent of n-propylbenzene. At 79C a small amount of distillate is collected. The standard vapor pressures of pure hexane is 812 mm and pure n-propylbenzene is 560 mm Hg, respectively, at 79C. Calculate the percentage of each of the two components in this fraction of distillate. Show your calculations. A copy of the In-Lab and Post-Lab Sections of the Final Report Grading Sheet is on the next page.

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InLab and PostLab Sections - Final Report:

Accuracy and completeness of OBSERVATION/DATA section Boiling points corrected for barometric pressure

8 8

RESULTS/DISCUSSION Overall organization, readability, completeness 8

Five plots of corrected distillation temperature versus distillation 5volume 2 Identification of your two unknown liquids in your distillation mixture 25 Discussion of simple versus fractional distillation; Do the results 6 1 support pr PostLab Question 10 100

Total for Final Report

72