Technique 8 STEAM DISTILLATION The simple and fractional distillations desctibed in Techniques 6 and 7 are applicable to completely soluble (miscible) mixtures only. When liquids are not mutually soluble (that is, are immiscible), they can also be distilled. A mixture of immiscible liquids will boil at a lower temperature than the boiling points of any of the separate components as pure compounds. When steam is used to provide one of the immiscible phases, the process is called steam distillation. ‘The advantage of this technique is that the desired material distlls at a temper- ature below 100 °C. Thus, if unstable or very high-boiling substances are to be removed from a mixture, decomposition is avoided. Since all gases mix, the two substances can mix in the vapor and codistill. Once the distillate is cooled, the desired component, which is not miscible, separates from the water. Steam distillation is used widely in isolating liquids and solids from natural sources. It js also used in removing a reaction product from a tarry reaction mixture. 8.1 DIFFERENCES BETWEEN DISTILLATION OF MISCIBLE AND IMMISCIBLE MIXTURES MISCIBLE Pang = PANa + PN O) Two liquids A and B that are mutually soluble (miscible) and that do not interact form an ideal solution and follow Raoult’s law, as shown in equation (1). One notes that the vapor pressures of pure liquids P,° and P,° are not added directly to give the total pressure Py but are reduced by the respective mole fractions N, and Ny. The total pressure above a miscible or a homogene- us solution will depend on P,° and P,? and also N, and Ng. Thus, the compo- sition of the vapor will also depend on both the vapor pressures and the mole factions of each component. mee Pra = Pa + Pa? @ On the other hand, when two mutually insoluble (immiscible) liquids are “mixed” to give a heterogeneous mixture, each exerts its own vapor pressure, independently of the other, as shown in equation (2). The mole fraction term does not appear in this equation, since the compounds are not miscible. One simply adds the vapor pressures of the pure liquids P,° and F,° at a given temperature to obtain the total pressure above the mixture. When the total pressure equals 760 mm, the mixture boils. The composition of the vapor from an immiscible mixture, in contrast to the miscible mixture, is determined only by the vapor pressures of the two substances codistilling, Equation (3) defines the composition of the vapor from an immiscible mixture. Calculations involv- ing this equation are given in Section 8.2. 541 Escaneado con CamScanner542 TECHNIC, Mey Moles A _ P® Moles B ~ Pr 9 A mixture of two immiscible liquids boils at a lower temperature than the boiling points of either component. The explanation for this behavior is like that given for minimum-boiling azeotropes (Technique 7, Section 7.7). One may hold that immiscible liquids behave as they do because an extreme incom- patibility between the two liquids leads to higher combined vapor pressures than Raoult’s law would predict. The higher combined vapor pressures cause a lower boiling point for the mixture than for either single component. Thus, one may think of steam distillation as a special type of azeotropic distillation, in which the substance is completely insoluble in water. The differences in the behavior of miscible and immiscible liquids, where Px? equals P,9, are shown in Figure 8-1. One notes that with miscible liquids, the composition of the vapor depends on the relative amounts of A and B present (Figure 8-1A). Thus, the composition of the vapor must change during a distillation. In contrast, the composition of the vapor with immiscible liquids is independent of the amount of A and B present (Figure 8-1B). Hence, the vapor composition must remain constant during the distillation of such liquids, as predicted by equation (3). Immiscible liquids act as if they were being dis- tilled simultaneously from separate compartments, as shown in Figure 8-1B, even though in practice they are “mixed” during a steam distillation. Since all gases mix, they do give rise to a homogeneous vapor and codistill. 8.2 IMMISCIBLE MIXTURES: CALCULATIONS We have stated that the composition of a distillate is constant during a steam distillation. This would also require that the boiling point of the mixture be constant. The boiling point of the mixtures will be below the boiling points of water (100 °C) and the pure substance. Some representative boiling points sacl ste ance ie © ©| | OOO }wor! ® ©| | @ 14 11 | 14 ®OG| (600G,,,,,, 0 FOO 600| (©000/""ool00 Ligui: Moles A> B Liguid: Moles Vapor: Moles A=B Vapor: Moles ASB Vapor: Moles A = B Py = PyINy + Py'Np PrePyt + Pye on sp to hd 8 net Ano kn 8 FIGURE 8-1. Total pressure behavior for miscible and immiscible liquids. 4, Ideal miscible liquids follow Raoult’ law: #, depends on the mole fractions and vapor pressures of A and 8; B, Immiscible liquids do not follow Raoult’s law: P, depends only on the vapor pressures of A and B. a Escaneado con CamScannerTEAM DISTILLATION 543 TABLE 8-1, BOILING POINTS AND COMPOSITIONS OF STEAM DISTILLATES BOILING POINT BOILING PoINT | COMPOSITION MIXTURE, OF PURE SUBSTANCE (°C) | OF MIXTURE (*C) | (% WATER) ‘Benzene-Water 80.1 60.4 8.9% Toluene-Water 110.6 850 20.2% Hexane-Water 69.0 616 5.6% Heptene-Water 98.4 79.2 12.9% Octane-Water 125.7 89.6 25.5% Nonane-Water 150.8 95.0 39.8% 4-Octanol-Water 195.0 99.4 90.0% and compositions of steam distillates are given in Table 8-1. Note that the higher the boiling point of a pure substance, the more closely the temperature _of the steam distillate approaches, but does not exceed, 100 °C. A substance may be codistilled with water at a temperature below 100 °C. This avoids the decomposition that might otherwise result at high temperatures with a simple distillation. For immiscible liquids, the molar proportions of two components in @ distillate equal the ratio of their vapor pressures in the boiling mixture, as given in equation (3). When the general equation (3) is rewritten for an immiscible mixture involving water, equation (4) results. Equation (4) can be modified by substituting the relation moles = (weight/molecular weight), to give equa- tion (5). Moles substance — Poiretance 4) Moles water ~~ Poy We substance _ (Phun) Molecular Weightypranes) 6) ‘Wt water ~~ —(P2.,,,)(Molecular weight,, at.) Consider, as a sample calculation, the steam distillation of 1-octanol. From Table.8-1, you see that the mixture boils at 99.4 °C. From a handbook, one obtains the vapor pressure of pure water at 99.4 °C (744 mm). Since Pia. must equal 760 mm, the vapor pressure of I-octanol-at 99.4 °C must equal 16 mm. Equation (5) is now solved as follows: We L-octanol _ (16)(130) _ ‘Wt water (744y(18) Thus, 0.155 g of 1-octanol codistills with each gram of water, It will require 100 g of water to remove 15.5 g of 1-octanol from a distilling flask. The distillate will have the calculated composition of 87% water and 13% 1-octanol, which is very close to the experimental value given in Table 8-1. 0.155 gram/gram water 8.3 STEAM DISTILLATION: METHODS Two methods for steam distillation are generally used in the laboratory. The first method uses live steam, from a steam line, passed into the flask con- taining the compound, In the second method, steam is generated in situ by heating a flask containing the compound and water. Escaneado con CamScannery 544 TECHNIQy, 1 A. Live Steam Method ‘The method with live steam is the most widely used, especially with high. molecular-weight (low-vapor-pressure) substances. It can even be used with volatile solids. The apparatus is assembled as shown in Figure 8-2. A piece of 6-mm glass tubing is bent to fit the flask and serves as a steam-inlet tube. The ground-glass joints must be lubricated, and the apparatus must be fastened securely to a ring stand, During the distillation, the joint between the condenser and the distilling head sometimes separates due to vibration. If this happens, vapor Will be lost unless the joint is immediately resealed. The distilling flask should never be filled more than half-full. The flask should be placed about 15 cm above the desk top. This distillation method does not usually require an external heating source, since the mixture is maintained at the boiling point with steam, Sometimes the distilling flask may begin to fill with water during the distillation. If this happens, it may be necessary to use a heating source such as a Bunsen burner to heat the liquid to its boiling point. The heat from the burner should be dispersed by means of a wire gauze. The entering steam helps to prevent bumping of the mixture. The Claisen head helps to reduce the possibility that material will be transferred to the receiving flask through exces- sive bumping. As shown in Figure 8-2, a steam-water trap must be placed in the steam line. When the steam valve is first turned on, a large amount of water (conden- sate) comes out of the valve. To prevent this condensate from entering the distilling flask and filling it with water, one must open the screw clamp on the trap fully so water can drain before reaching the flask. Once the water is drained, steam will begin to enter the distilling flask. The screw clamp on the live stearh trap ‘compound to be distilled screw clamp to allow condensed water to drain ice bath FIGURE 8-2. Steam distilation, using live steam aa i 4 Escaneado con CamScannereon DISTILLATION 545 Compound and boiling water— 7 wire gauze wood blocks Z- Baa=>> FIGURE 8-3. Direct steam distillation trap may then be closed. Occasionally, the clamp should be opened to allow condensate to be removed during the distillation. An ice bath increases the efficiency of the condensation of the distillate in the receiving flask. One should adjust the rate of flow of the steam so that vapor passes into the condenser as quickly as possible but continues to be condensed. The flow of cooling water through the condenser should be faster than in other types of distillations, to help cool the vapor. The vacuum adapter should be cool to the touch during the distillation. The condensate will be cloudy while the steam volatile material is distilling. The substances that codistll will separate on cooling, to give this cloudiness. Once the distillate is clear, the distillation is nearly complete. It is considered good practice to remove at least 10 mL more distillate after this point. When the distillation is to be stopped, the screw clamp on the steam trap ust be opened completely and the steam inlet tube must be removed from the distilling flask. If this is not done, the liquid will back up into the tube and steam trap. B. Direct Method The direct method is experimentally more convenient. Steam is produced in the distilling flask (in situ) by heating water to the boiling point in the presence of the compound to be distilled (Figure 8-3). As the steam is removed with the compound, water is added dropwise from the separatory funnel. This method works well for volatile liquids or for small amounts of material. It is mainly used for mixtures that do not have solids present. Solids may cause Escaneado con CamScanner546 TECHNIQUE 9 excessive bumping, In addition, foaming may be more troublesome. The live- steam method often eliminates these two problems. PROBLEMS 1, Calculate the weight of benzene codistilled with each gram of water and the percentage composition of the vapor produced during a steam distillation. The boiling point of the mixture is 69.4 °C. The vapor pressure of water at 69.4 °C is 227.7 mmHg. Compare the result with the data in Table 8-1. 2. Calculate the approximate boiling point of a mixture of bromobenzene and water at atmospheric pressure. A table of vapor pressures of water and bromobenzene at various temper- atures is given. VAPOR PRESSURES (mm) TEMPERATURE (°C) Water Bromobenzene 93 588 110 94 611 114 95 634 118 96 657 122 97 682 127 98 707 131 99 733 136 3. Calculate the weight of nitrobenzene that codistills (bp 99 °C) with each gram of water during a steam distillation. You may need the data given in the previous problem. 4. A mixture of p-nitrophenol and o-nitrophenol can be separated by steam distillation. The o-nitrophenol is steam-volatile while the para isomer is not volatile. Explain. Base your answer on the ability of the isomers to form hydrogen bonds internally. Escaneado con CamScanner