Water-Phenol Miscibility Diagram

Purpose Liquid water and phenol show limited miscibility below 70C. In this experiment, miscibility temperatures of several water-phenol mixtures of known composition will be measured. The phase coexistence line (miscibility temperature versus composition) will be determined, and the critical composition and temperature calculated. An extension of the experiment will be to measure the effect of a third component on the water-phenol critical point. Introduction Phenol, also known as carbolic acid, hydroxybenzene and phenyl alcohol, is produced at the rate of millions of tons per year, mostly from isopropyl benzene ("cumene"). Phenol is a starting material in the manufacture of plastics and drugs. It was used an antiseptic beginning in the 1860's. However, phenol is poisonous. The phenol-water mixtures used in this lab are concentrated and dangerous by contact or ingestion. Aqueous phenol solutions have been used pharmaceutically.1 As the diagram at right indicates, at low and high percentages of phenol, water and phenol mix completely, forming a single liquid phase. However, at intermediate compositions (and below the critical temperature) mixtures of phenol and water separate into two liquid phases. Point "h" in the figure is the critical point. Above the critical temperature, phenol and water are completely miscible. The water-phenol phase diagram contains a solid and water. This diagram is from Martin's Physical Pharmacy and Pharmaceutical Sciences. phase at high percent phenol, near and somewhat above room temperature. That part of the diagram is not shown in the Figure 2 and will not be explored in this experiment. The independent variable in the phase diagram is composition. Composition is sometimes given as mass percent, as in Figure 2, especially in older literature. This experiment will refer to composition as mole fraction phenol. Recall the definition of mole fraction. phenolwatersalt.odt 1
Figure 2: The liquid-liquid phase diagram of phenol

Figure 1: phenol

moles phenol total moles When only phenol and water are present, total moles means moles phenol plus moles water. x phenol= The first part of the experiment use tubes that contain known masses of water and phenol. For each tube, from the masses the mole fraction xphenol can be calculated. (Each tube also contains a little air mixed with water and phenol vapor, but the gas phase is ignored in this experiment.) At room temperature, a tube contains two liquid phases, one more dense than the other. The tube is heated in a water bath until the two phases merge. The temperature at which they merge is the "clearing temperature," also known as the "cloud" temperature, and lies on the liquid-liquid coexistence line. By using several sample tubes, one obtains several (xphenol, t) points on the coexistence line. We will fit a curve through those points, differentiate the curve to find its maximum, and use the maximum as the critical temperature, tc.

Figure 3: Sample (x,t) data and curve.

Even small concentrations of salts may have large affects on phase separation and the critical temperature. In aqueous solutions of organic molecules or polymers, salt may be added to make the organic material form a phase separate from the salty aqueous phase. This procedure may be familiar as "salting out." The miscibility of phenol and water is reduced by addition of many common salts such as alkali and alkaline-earth halides.2,3 The origin of the effect is the tendency of water molecules to associate with ions, hydrating them. In that way, simple ions reduce the tendency of water to solvate phenol. The result of adding salt is often an increased critical temperature and greater xphenol on the phenol-rich side of the coexistence curve. The salt effect will be studied by preparing a set of phenol-water samples of constant salt composition. Clearing temperatures observed in the water bath give a coexistence curve. From the coexistence curve, tc and xphenol can be determined in the presence of salt. The critical point with salt can then be compared to that obtained with phenol and water only.

phenolwatersalt.odt

Chemicals and Apparatus Phenol is in the hood. Each group needs about 10 grams of phenol. Waste phenol must go in the phenol-water waste bottle. CAUTION from the Material Safety Data Sheet (MSDS): When phenol touches your skin it can cause it to swell, burn, peel, and break out in hives. Phenol can cause cold sweats, convulsions, circulatory collapse, coma and even death. USE GLOVES. DO NOT INGEST PHENOL. A water bath is set up in the lab. Also in the lab: a digital thermometer 4-mL sample vials for phenol-water-salt solutions PTFE tape for sealing sample vials Solid salts: NaCl KCl KBr CaCl22H2O formula mass (g/mol) 58.4 74.6 119 111+36=147 (Note that adding this salt will also slightly increase moles water.)

Mass data for the prepared and numbered sample tubes: Sample tube phenol (grams) water (grams) 20 21 22 23 24 25 26 27 28 0.553 0.624 0.876 1.206 1.431 1.616 2.047 2.236 2.421 3.461 3.379 3.107 2.813 2.605 2.394 1.954 1.758 1.613

phenolwatersalt.odt

Experimental Procedure Start with the water bath below 40C. The bath temperature should not have to exceed 85C during the experiment. Turn on the digital thermometer and immerse the end of its thermocouple in the water bath. Turn on the heater-stirrer to raise the bath temperature. Several numbered sample tubes should be in the plastic rack in the water. Place the rack in the water bath. The water level should be at or near the bottoms of the tubes' caps. Add water to the bath if necessary. Each of the tubes will initially show two phases. The lower layer is richer in phenol, the upper is richer in water. As the sample tubes warm, their caps may loosen. Tighten the caps once or twice during the experiment, to prevent phenol from leaking out into the water bath. If a cap will not tighten sufficiently, or if leakage occurs, then prepare a replacement sample tube. To do that: measure similar masses of phenol and water into a fresh sample tube, wrap its threads twice around with PTFE tape, and write a new sample number on its cap. Record the phenol and water masses in the laboratory so future lab groups will know them. Raise the temperature of the water bath. As the temperature rises, watch for sample tubes approaching miscibility. You may notice cloudiness in the tube, or a blurring of the phase boundary. Pick each of the tubes in turn. Use a test-tube holder to immerse the tube completely and shake it to stir the contents. (This is the point at which the tube's cap must seal tightly.) Record the temperature, to the nearest 0.1C, at which the two liquid phases mix. You may want to lower the bath's temperature at times, to check or better locate a clearing temperature. That is easily done by running cold water through the cooling coils of the heater/stirrer. After recording the clearing temperature for all of the small tubes, remove the rack of tubes from the water bath. Place the tubes securely in a container in the refrigerator. Choose a salt to study. Choose a mole fraction salt. For a 1:1 salt, xsalt=0.0002=210-4 might be good. For a 1:2 salt (e.g., CaCl2) xsalt should be smaller, perhaps 110-4. Make several (e.g., five) sample vials of phenol and water, with mole fraction phenol running between 0.025 and 0.25. Here is a method to make a vial. Choose a target mole fraction phenol, xp. Plan to fill each vial to a total mass of 4.0 grams. m p / 94.11 Note that x p = , where 94 and 18 are formula masses of phenol m p / 94.11 4.0 m p / 18.02 and water, and mp is the mass phenol to put in the tube. Solve for mp. (A sample calculation is below.) phenolwatersalt.odt 4

Tare an empty sample vial on the balance. Add mp grams of phenol to the empty vial. Add water to the vial until the total mass of the contents is 4.0 grams. From the actual masses of water and phenol in the vial, calculate the moles of phenol and the moles of water. Calculate the moles of salt to add: n salt x salt n phenol n water . From moles salt, calculate the mass of salt to add, msalt=nsaltMsalt, where Msalt is the formula mass of the salt. Tare the vial again, then add the calculated mass of salt. Wrap PTFE tape twice around the threads of the vial. Screw the cap securely into place. Bearing in mind the poisonous nature of phenol, wipe up any spills near or on the balance.

Sample calculation: If a vial is to have xphenol=0.10 and xsalt = 0.0002, with the salt being KBr, then 94 4.0 94 m p = 4.0grams = = 1.47 g 94 18 0.9 / 0.1 1 xp 94 18 xp If the actual mass of phenol added is 1.47 grams, then np = 1.47/94.1 = 0.0156. If the actual mass of water added is 4-1.47 = 2.53 g, the nw = 2.53/18.0 = 0.1406. Then the total moles of phenol and water is ntotal = 0.0156+0.1406 = 0.156. Suppose the mole fraction of salt is xsalt=0.0001. Then the mass of KBr to add is 0.0002 0.156 mol 119 g/mol = 0.0037 grams KBr.

phenolwatersalt.odt

Calculation Procedure Analyze the clearing-temperature data from the small vials of phenol and water as follows. Calculate mole fraction phenol, xphenol, for each of the several tubes. Make a table of mole fraction and clearing temperature. Graph the clearing temperature versus mole fraction, as in Figure 3. Fit a cubic equation t = a b x phenol c x 2 d x3 phenol phenol

(10) through the data points. This can be done using Excel's regression, which is under the data analysis menu. Regression is an Excel "add-in," so it may have to be added in before it can be used. To do a cubic fit using regression, first prepare columns of x, x2, x3 and t values. For example, t x x2 x3 53.0 58.9 66.8 67.8 64.4 59.9 0.0270 0.0350 0.0690 0.1050 0.1500 0.1960 7.29E04 1.24E03 4.80E03 1.10E02 2.26E02 3.84E02 1.97E05 4.36E05 3.33E04 1.16E03 3.39E03 7.52E03

54.5 0.2230 4.98E02 1.11E02 When doing the regression calculation, the t column contains the "y" values. The "x values" consist of all three columns: x, x2 and x3. Use your own data, of course, not the sample data tabulated above. To find the critical temperature, differentiate the cubic equation and set the derivative to zero, to find its maximum. That is, take the derivative of t, equation 10. Set the resulting quadratic equation to zero. Solve for its roots. Use the roots to calculate the maximum t. The maximum t is the critical temperature, tc. The xphenol at which t is maximum should be the critical mole fraction. The main result of this experiment is the critical point, (xphenol , tcritical). Find literature values of the critical temperature and composition and compare your results to the literature values. Literature values are available from sources such as references 2-7. Analyze data from the phenol-water-salt sample vials Analyze the data as you did for the pure phenol-water sample vials. Graph clearing temperature versus xphenol. Fit a cubic equation through the data. Find the critical temperature and the critical mole fraction. Make a graph of clearing temperature versus xphenol, showing both water-phenol and water-phenol-salt data on the same graph. Your discussion should describe and discuss the effect of salt added to the phenol-water mixture.

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References 1. Sinko, Patrick J., Martin's Physical Pharmacy and Pharmaceutical Sciences, 5th ed., Lippincott Williams & Wilkins, 2005. page 51. 2. Singh, Man "Upper critical solution temperatures for immiscible solvent systems with halide salts, carboxylic acids, surfactants and polynuclear aromatic compounds and benzene derivatives," Journal of Chemical Thermodynamics, 39, 240-246, 2007. 3. Ghizellaoui, S; Meniai, A.-H. "Experimental study and modeling of the salt effect on phase equilibria for binary hydroxylic liquid systems," Desalination, 185, 457-472, 2005. 4. International Critical Tables of Numerical Data, Physics, Chemistry and Technology, published for the National Research Council by the McGraw-Hill Book Company, Inc.: New York and London, 1928; Volume III, page 365. The table shows mass percent phenol. 5. Bowden, S.T. The Phase Rule and Phase Reactions, MacMillan, 1950, p.105. 6. Campbell, Alan N.; Campbell, A. Jean R. "Concentrations, total and partial vapor pressures, surface tensions and viscosities, in the systems phenol-water and phenol-water-4% succinic acid," Journal of the American Chemical Society, 59(12), 2481-2488, 1937. Percents and x in this paper are by mass, not by mole. 7. Singh, M. "Upper consolute temperature of water-phenol systems with some additives," Journal of the Iranian Chemical Society, 3(4), 334-339, 2006.

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