706 Part Two_The Techniques (a) 11,1 Trichloroethane (b) Hexane 6. A student prepares ethyl benzoate by the reaction of benzoic acid with ethanol using a sulfu- ric acid catalyst. The following compounds are found in the crude reaction mixture: ethyl benzoate (major component), benzoic acid, ethanol, and sulfuric acid. Using a handbook, obtain the solu- bility properties in water for each of these compounds (Technique 20, Section 20.1, p. 861). Indicate how you would remove benzoic acid, ethanol, and sulfuric acid from ethyl benzoate. At some point in the purification, you should also use an aqueous sodium bicarbonate solution 77, Calculate the weight of water that could be removed from a wet organic phase using 50.0 mg of magnesium sulfate. Assume that it gives the hydrate listed in Table 7.2, 8. Explain the following laboratory instructions in a procedure: (a) “Wash the organic layer with 5.0 mL. of 5% aqueous sodium bicarbonate.” (b) “Extract the aqueous layer three times with 2-mL portions of methylene chloride." 9, Just prior to drying an organic layer with a drying agent, you notice water droplets in the or- ‘ganic layer. What should you do next? 10, What should you do if there is some question abont which layer is the organic one during an extraction procedure? 11, Saturated aqueous sodium chloride (d= 1.2 g/mL) is added to the following mixtures in or- det to dry ihe organic layer. Which layer is likely to be on the bottom in each case? (@) Sodium chloride layer or a layer containing a high-density organic compound dissolved in methylene chloride (d = 1.4 g/mL) (b) Sodium chloride layer or a layer containing a low-density organic compound dissolved in methylene chloride (d = 1.1 g/mL) TECHNIQUE 8 a Simple Distillation Distillation is the process of vaporizing a liquid, condcusing the vapor, and collect. ing the condensate in another container. This technique is very useful for separating a liq- ‘uid mixture when the components have different boiling points, or when one of the com- ponents will not distill. It is one of the principal methods of purifying a liquid. Four basic distillation methods are available to the chemist: simple distillation, vacuum distillation (distillation at reduced pressure), fractional distillation, and steam distillation. This tech- nique chapter will discuss simple distillation. Vacuum distillation will be discussed in Technique 9. Fractional distillation will be discussed in Technique 10, and steam distilla- tion will be discussed in Technique 11. 8.1 THE EVOLUTION OF DISTILLATION EQUIPMENT There are probably more types and styles of distillation apparatus than exist for any other technique in chemistry. Over the centuries, chemists have devised just about every conceivable design. The earliest known types of distillation apparatus were the alembic and the retort (Fig. 8.1). They were used by alchemists in the Middle Ages and theTechnique 8 Simple Distillation 707 Dieting ‘chemical equipment C3 2.1600 Modern microscale organi lab Kt Consenser - ckman tH 1905, Figure 8.1 Some stages in the evolution of distillation equipment from alchemical equip- ment (dates represent approximate time of use). Renaissance, and probably even earlier by Arabic chemists. Most other distillation equip- ment has evolved as variations on these designs. Figure 8.1 shows several stages in the evolution of distillation equipment as it re- lates to the organic laboratory. It is not intended to be a complete history; rather, it is rep- resentative, Up until recent years, equipment based on the retort design was common in the laboratory. Although the retort itself was still in use early in this century, it had evolved by that time into the distillation flask and water-cooled condenser combination. This early equipment was connected with drilled corks. By 1958, most introductory laboratories were beginning to use “organic lab kits” that included glassware connected by standard-taper glass joints. The original lab kits contained large 24/40 joints. Within a short time, they became smaller with F 19/22 and even’ 14/20 joints. These later kits are still being used today in many “macroscale” laboratory courses such as yours,708 Part Two The Techniques In the 1960s, researchers developed even smaller versions of these kits for working at the “microscale” level (in Fig. 8.1, see the box labeled 1965, research use only), but this glassware is generally too expensive to use in an introductory laboratory. However, in the mid 1980s, several groups developed a different style of microscale distillation equipment based on the alembic design (see the box labeled 1985, Hickman still). This new microscale equipment has 14/10 standard-taper joints, threaded outer joints with screweap connectors, and an internal O-ring for a compression seal, Microscale equip- ‘ment similar to this is now used in many introductory courses. The advantages of this glassware are that there is less material used (lower cost), lower personal exposure to chemicals, and less waste generated. Because both types of equipment are in use today, after we describe macroscale equipment, we will also show the equivalent microscale dis- tillation apparatus. 8.2 DISTILLATION THEORY In the traditional distillation of a pure substance, vapor rises from the distillation flask and comes into contact with a thermometer that records its temperature. The vapor then passes through a condenser, which reliquefies the vapor and passes it into the re- ceiving flask. The temperature observed during the distillation of a pure substance re- ‘mains constant throughout the distillation so long as both vapor and liquid are present in the system (see Fig. 8.2A). When a liquid mixture is distilled, often the temperature does not remain constant but increases throughout the distillation. ‘The reason for this is that the composition of the vapor that is distilling varies continuously during the distillation (see Fig. 8.2B). For a liquid mixture, the composition of the vapor in equilibrium with the heated solution is different from the composition of the solution itself. This is shown in Figure 8.3, which is a phase diagram of the typical vapor-liquid relation for a two-component system (A + B). Aon A+B Time—> Time——> Time——> A B c Figure:8.2. Thee types of temperature behavior during'e simple distillation. (A) A single Pure component. (B) Two. components of similar boiling points. (C) Two components with widely differing boiling points. Good separations are achieved in A and C,Technique 8 Simple Distillation 709 ‘A 100% — 80% — 60% — 40% — 20% — 0% 0% — 20% —40% —60%— 80% —100% B Figure 8.3 Phase diagram for a typical liquid mixture of two components. On this diagram, horizontal lines represent constant temperatures. The upper curve Tepresents vapor composition, and the lower curve represents liquid composition. For any horizontal line (constant temperature), like that shown at f, the intersections of the line with the curves give the compositions of the liquid and the vapor that are in equilibrium with each other at that temperature. In the diagram, at temperature 1, the intersection of the curve at x indicates that liquid of composition w will be in equilibrium with vapor of ‘composition z, which corresponds to the intersection at y. Composition is given as a mole percentage of A and B in the mixture. Pure A, which boils at temperature fa, is repre- sented at the left. Pure B, which boils at temperature fp, is represented on the right. For either pure A or pure B, the vapor and liquid curves meet at the boiling point. Thus, ei- ther pure A or pure B will distill at a constant temperature (fq or fy). Both the vapor and the liquid must have the same composition in either of these cases. This is not the case for mixtures of A and B. A mixture of A and B of composition w will have the following behavior when heated, The temperature of the liquid mixture will increase until the boiling point of the mixture is reached. This corresponds to following line wx from w to x, the boiling point of the mixture #. At temperature ¢ the liquid begins to vaporize, which corresponds to line xy. The vapor has the composition corresponding to z. In other words, the first vapor ob- tained in distilling a mixture of A and B does not consist of pure A. It is richer in A than the original mixture but still contains a significant amount of the higher boiling compo- nent B, even from the very beginning of the distillation. The result is that it is never pos- sible to separate a mixture completely by a simple distillation. However, in two cases it is possible to get an acceptable separation into relatively pure components. In the first case, if the boiling points of A and B differ by a large amount (>100°), and if the distil- lation is carried out carefully, it will be possible to get a fair separation of A and B. In the second case, if A contains a fairly small amount of B (<10%), a reasonable separa- tion of A from B ‘can be achieved. When the boiling-point differences aré nét latge, and! when highly pure components are desired, it is necessary to perform a fractional distil-710 Part Two The Techniques Jation. Fractional distillation is described in Technique 10, where the behavior during a simple distillation is also considered in detail. Note only that as vapor distils from the mixture of composition w (Fig, 8.3), it is richer in A than is the solution. Thus, the com- ponition of the material left behind in the distillation becomes richer in B (moves to the Fieht from w toward pure B in the graph). A mixture of 90% B (dotted Tine on the right side in Fig, 8.3) has a higher boiling point than at w. Hence, the temperature of the lig- tid in the distillation flask will increase during the distillation, and the composition of the distillate will change (as is shown in Fig. 8.2B). When two components that have a large boiling-point difference are distilled, the temperature remains constant while the first component distils. Ifthe temperature remains Constant, a relatively pure substance is being distilled. After the first substance distill, the temperature of the vapors rises, and the second component distills, again at a constant temperature. This is shown in Figure 8.2C. A typical application of this type of distiie: tion might be an instance of a reaction mixture containing the desired component A (bp 140°C) contaminated with a small amount of undesired component B (bp 250°C) and mixed with a solvent such as diethyl ether (bp 36°C). The ether is removed easily at low temperature. Pure A is removed at a higher temperature and collected in a separate fe- ceiver, Component B can then be distilled, but it usually is left as a residue and not dis- tiled. This separation is not difficult and represents a case where simple distillation might be used to advantage. 8.3 SIMPLE DISTILLATION—STANDARD APPARATUS For a simple distillation, the apparatus shown in Figure 8.4 is used. Six pieces of specialized glassware are used: 4, Distilling flask 2, Distillation head 3, Thermometer adapter 4, Water condenser 5. Vacuum takeoff adapter 6, Receiving flask ‘The apparatus is usually heated electrically, using a heating mantle. The distilling flask, condenser, and vacuum adapter should be clamped. Two different methods of clamping this apparatus were shown in Technique 3 (Fig. 3.4, page 616 and Fig, 3.6, page 617) ‘The receiving flask should be supported by removable wooden blocks or a wire gauze on an iron ring attached to a ring stand. The various components are each discussed below, along with some other important points. Distilling Flask. The distilling flask should be a round-bottom flask. This type of flask is designed to withstand the required input of heat, and to accommodate the boiling action It gives a maximized heating surface. The size ofthe distilling flask should be cho- sen so that it is never filled more than two-thirds full. When the flask is filled beyond this point, the neck constricts and “chokes” the boiling action, resulting in bumping. The sur-Technique 8 Simple Distillation 711 ‘Thermometer +h adapter Distiting head Figure 8.4 Distillation with the standard macroscale lab kit. face area of the boiling liquid should be kept as large as possible. However, too large a distilling flask should also be avoided. With too large a flask, the holdup is excessive; the holdup is the amount of material that cannot distill since some vapor must fill the empty flask. When you cool the apparatus at the end, this material drops back into the distilling flask. Boiling Stones. A boiling stone (Technique 3, Section 3.6, page 622) should be used uring distillation to prevent bumping. As an alternative, the liquid being distilled may be rapidly stirred using a magnetic stirrer and stir bar (Technique 3, Section 3.5, page 621). If you forget a boiling stone, cool the mixture before adding it. If you add a boiling stone to a hot superheated liquid, it may “erupt” into vigorous boiling, breaking your appara- tus and spilling hot solvent everywhere. Grease. In most cases, it is unnecessary to grease standard-taper joints for a sim- ple distillation. The grease makes cleanup more difficult, and it may contaminate your product. Distillation Head. The distillation head directs the distilling vapors into the condenser and allows the connection of a thermometer via the thermometer adapter. The thermometer should be positioned in the distillation head so that it is placed directly in the stream of va-712 Part Two The Techniques por that is distilling. This can be accomplished if the entire bulb of the thermometer is po- sitioned below the side am of the distilling head (see the circular inset in Fig. 8.4). The en- tire bulb must be immersed in the vapor to achieve an accurate temperature reading. When distilling, you should be able to see a reflux ring (Technique 3, Section 3.4, page 619) po- sitioned well above both the thermometer bulb and the bottom of the side arm. ‘Thermometer Adapter. The thermometer adapter connects to the top of the dis- tillation head (see Fig. 8.4). There are two parts to the thermometer adapter: a glass joint with an open rolled edge on the top, and a rubber adapter that fits over the rolled edge and holds the thermometer. The thermometer fits in a hole in the top of the rubber adapter and can be adjusted upward and downward by sliding it in the hole. Adjust the bulb to a point below the side arm, Water Condenser. The joint between the distillation head and the water condenser is the joint most prone to leak in this entire apparatus. Since the distilling liquid is both hot and vaporized when it reaches this joint, it will leak out of any small opening between the two joint surfaces. The odd angle of the joint, neither vertical or horizontal, also makes a good connection more difficult. Be sure this joint is well sealed. If possible, use one of the plastic joint clips described in Technique 3, Figure 3.5, page 617. Otherwise, adjust your clamps to be sure that the joint surfaces are pressed together, and not pulled apart. The condenser will remain full of cooling water only if the water flows upward, not downward. The water input hose should be connected to the lower opening in the jacket, and the exit hose should be attached to the upper opening. Place the other end of the exit hose in a sink. A moderate water flow will perform a good deal of cooling. A high rate of water flow may cause the tubing to pop off the joints and cause a flood. If you hold the exit hose horizontally and point the end into a sink, the flow rate is correct if the wa- ter stream continues horizontally for about two inches before bending downward. If a distillation apparatus is to be left untended for a period of time, it is a good idea to wrap copper wire around the ends of the tubing and twist it tight. This will help to pre- vent the hoses from popping off of the connectors if there is an unexpected water pres- sure change. ‘Vacuum Adapter. In a simple distillation the vacuum adapter is not connected to a vacuum, but is left open. It is merely an opening to the outside air so that pressure does not build up in the distillation system. If you plug this opening, you will have a closed system (no outlet). It is always dangerous to heat a closed system. Enough pressure can build up in the closed system so that it can explode. The vacuum adapter, in this case, merely directs the distillate into the receiving, or collection, flask. If the substance you are distilling is water sensitive, you can attach a calcium chlo- ride drying tube to the vacuum connection to protect the freshly distilled liquid from at- mospheric water vapor. Air that enters the apparatus will have to pass through the calcium chloride and be dried. Depending on the severity of the problem, drying agents other than calcium chloride may also be used, ‘The vacuum adapter has a disturbing tendency to obey the laws of Newtonian physics ‘and fall off the slanted condenser onto the desk and break. If they are available, it is a {200d idea to use plastic joint clips on both ends of this piece. The top clip will secure the vacuum adapter to the condenser, and the bottom clip will secure the receiving flask, pre- venting it from falling.Technique 8 Simple Di 3 Rate of Heating. The rate of heating for the distillation can be adjusted to the proper rate of takeoff, the rate at which distillate leaves the condenser, by watching drops of liquid emerge from the bottom of the vacuum adapter. A rate of from one to three drops per second is considered a proper rate of takeoff for most applications. At a greater rate, equilibrium is not established within the distillation apparatus, and the separation may be poor. A slower rate of takeoff is also unsatisfactory since the temperature recorded on the ‘thermometer is not maintained by a constant vapor stream, thus leading to an inaccurately low observation of the boiling point. Receiving Flask. The receiving flask collects the distilled liquid, and is usually a round-bottom flask. If the liquid you are distilling is extremely volatile, and there is dan- ger of losing some of it to evaporation, it is sometimes advisable to coo! the receiving flask in an ice-water bath, Fractions. The material being distilled is called the distillate, Frequently a distil- late is collected in contiguous portions, called fractions. This is accomplished by replac- ing the collection flask with clean ones at regular intervals. If a small amount of liquid is collected at the beginning of a distillation and not saved or used further, it is called a fore- run, Subsequent fractions will have higher boiling ranges, and each fraction should be la- beled with its correct boiling range when the fraction is taken. For a simple distillation of a pure material, most of the material will be collected in a single large midrun fraction, with only a small forerun, In some small-scale distillations, the volume of the forerun will be so small that you will not be able to collect it separately from the midrun fraction. The ‘material left behind is called the residue. It is usually advised that you discontinue a dis- tillation before the distilling flask becomes empty. Typically, the residue becomes increas ingly dark in color during distillation, and it frequently contains thermal decomposition. products. In addition, a dry residue may explode on overheating, or the flask may melt or crack when it becomes dry. Don’t distill until the distilling flask is completely dry! 8.4 MICROSCALE AND SEMI-MICROSCALE EQUIPMENT When you wish to distill quantities that are smaller than 4-5 mL, different equip- ment is required. What you use depends on how small a quantity you wish to distill. A. SEMI-MICROSCALE One possibility is to use equipment identical in style to that used with conventional macroscale procedures, but to “downsize” it using F 14/10 joints. The major manufactur- ers do make distillation heads and vacuum takeoff adapters with 14/10 joints. This equip- ‘ment will allow you to handle quantities of from 5 to 15 mL. An example of such a “semi- microscale” apparatus is given in Figure 8.5. Although the manufacturers make T 14/10 condensers, the condenser has been left out in this example. This can be done if the ma- terial to be distilled is not extremely volatile or is high boiling. It is also possible to omit the condenser if you not have a large amount of material and can cool the receiving flask in an ice-water bath as shown in the figure.Thermometer bub ow Thecromeir apr UTI) oistation neaa [| Ul Bert yao VU ff adapter O suing tom Round — ar"? oto ack : Albock ( {age flo ea SALA too water iS ao | Thormameter bub L~,)} biewaateatne Figure 8,6 Basic microscale distillation. m4Technique 8 Simple Distillation 715 B. MICROSCALE—STUDENT EQUIPMENT Figure 8.6 shows the typical distillation setup for those students who are taking a microscale laboratory course. Instead of a distillation head, condenser, and vacuum takeoff, this equipment uses a single piece of glassware called a Hickman head. The Hickman head provides a “short path” for the distilled liquid to travel before it is col- lected. The liquid is boiled, moves upward through the central stem of the Hickman head, condenses on the walls of the “chimney,” and then runs down the sides into the circular well surrounding the stem. With very volatile liquids, a condenser can be placed on top of the Hickman head to improve its efficiency. The apparatus shown uses a 5-mL conical vial as the distilling flask, meaning that this apparatus can dis- till from 1 to 3 mL of liquid. Unfortunately, the well in most Hickman heads holds only about 0.5-1.0 mL. That means the well must be emptied several times. This is done using a disposable Pasteur pipet as shown in Figure 8.7. The figure shows two different styles of Hickman head. The one with the side port makes removal of the distillate easier. ‘Open and remove with pipet cap Side port ‘Open side port and. remove with pipet Figure 8.7. Two styles of Hickman head.716 Part Two The Techniques Figure 8.8 A research-style short-path distillation apparatus. . MICROSCALE—RESEARCH EQUIPMENT Figure 8.8 shows a very-well designed research-style, short-path distillation head. Note how the equipment has been “unitized,” eliminating several joints, and decreasing the holdup. PROBLEMS 1. Using Figure 8.3, answer the following questions. (@) What is the molar composition of the vapor in equilibrium with a boiling liquid that has a composition of 60% A and 40% B? (b) A sample of vapor has the composition 50% A and 50% B. What is the composition of the boiling liquid that produced this vapor? 2. Use an apparatus similar to that shown in Figure 8.4, and assume that the round-bottom flask holds 100 mL and the distilling head has an internal volume of 12 mL. in the vertical section. At the end of a distillation, vapor would fill this volume, but it could not be forced through the system. No liquid would remain in the distillation flask. Assuming this holdup volume of 112 mL, use the ideal gas law and assume a boiling point of 100°C (760 mm Hg) to calculate the number of milliliters of liquid (d = 0.9 g/mL, MW = 200) that would recondense into the distillation flask upon cooling. 3. Explain the significance of a horizontal line connecting a point on the lower curve with a point (on the upper curve (such as line 2) in Figure 8.3. 4, Using Figure 8.3, determine the boiling point of a liquid having a molar composition of 50% A and 50% B. . Where should the thermometer bulb be located in (a) a microscale distillation apparatus using a Hickman head? (b) a macroscale distillation apparatus using a distilling head, condenser, and vacuum takeoff adapter? 6. Under what conditions can a good separation be achieved with a simple distillation?