Crystallization

Revised 6/4/12

CRYSTALLIZATION
Crystallization is a common technique used to purify solids. Two common methods of crystallization are gradual cooling and diffusion. Gradual Cooling Gradual cooling involves dissolving the impure solid in a minimum amount of a hot solvent and allowing the resulting solution to cool slowly to room temperature. During the cooling process, pure (or almost pure) crystals form and are then collected by vacuum filtration. The first step in the crystallization process is to find an "ideal solvent by testing a small amount of the impure solid. The desired compound should be very soluble in the solvent when it is hot (near the boiling), but only slightly soluble at room temperature. Sometimes a solvent mixture (two or more solvents in a specific ratio) is required to achieve this temperature dependent solubility. At the same time, the dissolved impurities (byproducts and unreacted starting material) should be highly soluble in the solvent at BOTH high and low solvent temperatures. The compound must precipitate out of solution at cooler temperatures to allow its separation from the solvent and the dissolved impurities by filtration. The next step is to dissolve the solid to be purified in a minimum amount of hot solvent. This step should be performed quickly, with stirring if necessary. (Note: The solid and solvent should NOT be combined and then heated this may cause decomposition of the desired compound. The solvent should always be heated first, and then added to the solid.) For the largest and purest possible crystals, the resulting solution should be set in a location where it will not be agitated. The solubilities of three compounds in benzene as a function of temperature is shown in Figure 1. The following example illustrates how the relationship between temperature and solubility is used to isolate a desired compound by crystallization. A mixture of 5.0 g of A (an impurity), 20.0 g of B (the desired compound), and 3.0 g of C (an impurity) is combined with 100-mL of boiling benzene (75-80C). According to the solubility

Crystallization

Revised 6/4/12

diagram, all compounds will initially dissolve. Compound B begins to crystallize once the temperature drops below 67C. When the solution cools to 15C, all of A and C remain dissolved: their solubilities (17.5 g of A and 3.5 g of B per 100 mL benzene at 15C) are greater than the amounts of each present in solution (5.0 g of A, 3.0 g of C). However, at 15C the solubility of B is 7 g per 100 mL benzene, so only 7 grams of B remain dissolved and 13 g have crystallized out of solution. The purified yield of B (13 g) will be about 65%. An attempt to increase the yield of B by lowering the temperature below 15C would be ineffective because C, an impurity, would also begin to crystallize, contaminating B again. If more than 3.0 g of C were present the purified yield of B would be even lower. Why?

Benzene Solubilites of 3 Different Solids

55 50
25 22.5

Benzene Solubilites of 3 Different Solids

Solubility (g/100mL C6H6)

40 35 30 25 20 15 10 5 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75

Solubility (g/100mL C6H6)

45

20 17.5 15 12.5 10 7.5 5 2.5 0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75

Temperature (oC)

Temperature (oC)

Figure 1. Solubility Curves of A (), B (), and C() in benzene. Diffusion Crystallization by diffusion is an alternative to gradual cooling that does not use heated solvents. This crystallization process is preferable if the desired compound degrades at the elevated temperatures of solvent boiling points. The impure solid is dissolved in a minimum amount of a solvent in which it is highly soluble (the good solvent). This solution is placed in a test tube anchored at a 45 angle by a clamp (or leaned at a similar angle in a beaker). The next step is to carefully layer a solvent in which the desired compound is insoluble (the bad solvent) on the top of the first solution. The bad solvent is slowly delivered by disposable pipet that is in contact with the lowest edge of the test tube opening (Figure 2). Slow diffusion of the bad solvent into the good solvent will cause crystals to slowly grow at the interface between the two solvents. For diffusion to work, the impurities must be soluble in both solvents.

Crystallization

Revised 6/4/12

"Bad" Solvent

"Good" Solvent with dissolved Impure Product

Figure 2. Layering of Solvents for Diffusion Crystallization Review Questions: In the slow cooling crystallization process, is it possible to recover 100% of the desired product that is dissolved in a minimum amount of boiling benzene? (No) Assume 15 g of substance B is mixed with 5g of substance C in 100-mL of benzene (Fig 1). a) At what minimum temperature are BOTH substances completely dissolved? b) At what temperature range will B crystallize but all of C remains in solution? c) What is the mass and percent yield of B that is recovered as a crystallized solid if the benzene solution is heated to 65C and then cooled to 40C? ( (a) about 54C (b) 35 to 54C (c) about 3 g or 20% )