4.7 ISOLATION AND PURIFICATION OF SOLIDS 105 Contifuge id Centrifuge Centrifuge tube 5 Fppendort Figure 4.16: Centrifuge, Centrifugation generates much higher gravity forces in certain periods of time, allowing the separation of precipitates, suspended cells in biological fluids, etc., more efficiently than with conventional filtration. Although not a filtration technique, it can be used to separate impurities that are suspended within a liquid. 4.7.3. Recrystallization In a typical laboratory experiment, a solid that is separated from a reaction crude is usually accompanied by impurities, so that purification is necessary. By the technique called recrystallization, many solids can be purified using pure solvents or solvent mixtures. Recrystallization is based on the different solubility that a solid substance presents in a solvent at r-t. or when the solvent is hot. The recrystallization process is carried out with product loss, so the overall reaction yield is affected, The crucial point of the crystal that must mect the following properti tion process is the choice of the solvent * Total solubility of the substance to be purified at high temperatures. * Low capacity of dissolving the impuriti any temperature range. ‘that contaminate the product in ‘* Absence of chemical reaction with the product to be purified. * Generation of good crystals of the product to be purified, Easy removal. For practical purposes, two types of recrystallization can be distinguished: in water and in organic solvents. 1, Recrystallization from water: Many organic compounds are insoluble in water at r-t., but they are hot. For this purpose a suspension of the solid is106 4.7 ISOLATION AND PURIFICATION OF SOLIDS prepared in the minimum amount of water in a beaker or Exlenmeyer flask, and the mixture is brought to a boil. If the solid does not dissolve under ‘these conditions, small amounts are added and the water is boiled again until the compound dissolves. Note that suspended particles corresponding to part of the insoluble impurities often remain. If the solid is dark in color, the addition of small amounts of activated carbon will retain most of these colored impurities. ‘The procedure for recrystallization from water is as follows (see Fig- ure 4.17): * Transfer the solid for recrystallization to an Erlenmeyer or beaker. * Dissolve the substance in the minimum amount of hot solvent. ‘* If the starting crystals exhibit intense color due to the presence of impurities, add some activated carbon to remove them, since the colored impurities are retained in the activated carbon. ‘* Heat the mixture to boiling on a hot plate, checking that the prod- uct to recrystallize has been completely dissolved. Magnetic stirring should be performed (or add a boiling chip) to avoid sudden boiling and the formation of solid splashes. * Disconnect the hot plate. * Filter the hot solution by gravity using a conical funnel and fluted filter to remove insoluble impurities as well as activated carbon (dis- carding the solid residue, composed of activated carbon and insoluble impurities, on the fluted filter). Tweezers, tongs, or a piece of filter pa- per should be used when manipulating an Erlenmeyer flask or beaker to avoid burns when handling hot glass containers. * When the product solidifies in the funnel, add hot water. * As the solution cools, the corresponding product crystals will form (external cooling helps this process). * Finally, after the filtrate completely cools, these crystals are filtered under vacuum and washed (with the cold solvent used for recrystal- ization) in a Biichner to remove adhering filtrate and then dried to remove traces of solvent. In the case of incomplete crystallization, concentrate the filtrate (by heat- ing and by evaporating half of the solvent), and repeat the process Recrystallization in organic solvents: When a volatile organic solvent is used instead of water, the heating part of the solution is performed with a refiux assembly to prevent flammable volatile organic solvent vapors from causing fires. ‘The procedure for recrystallization is as follows:107 4.7 ISOLATION AND PURIFICATION OF SOLIDS ‘Ad activated carbon ‘organic solvent (rfl) the solid in a volatile 1A) Dissolve the solid in water 4) Crystallization {external cool) Figure 4.17: Stops in recrystallization.108 4.7 ISOLATION AND PURIFICATION OF SOLIDS # Set a round-bottom flask with a clamp and a connector on a hot plate « Transfer the solid to be recrystallized using a solid funnel or a pi of coated paper. * Add the solvent or solvent mixture and a boiling chip or a stir bar (if a magnetic stirring plate is available) * Attach a reflux condenser to the flask, connect the tubing, and open the water or cooling circuit. ‘* Heat the mixture to reflux to dissolve the solid. ‘¢ Tum off the heating plate and allow to cool in order to stop the reflux. * While the flask is still warm, gravity filter the contents of the flask, helping with tongs. © Cool the filtrate to r.t. and let stand until the end of the erystallizae tion of the solid. Sometimes crystallization is facilitated by seeding a few crystals of the product or scratching the bottom of the container with a glass rod. In both cases crystallization nuclei are generated, accelerating the process ‘The main reasons for failure with this technique are: * ‘The wrong solvent is chosen for the recrystallization, * The wrong amount of solvent is used to dissolve the recrystallization solid. * Lack of precipitation when the solution is cooled. © An oily substance formed instead of a solid precipitate. 4.7.4. Sublimation Sublimation or volatilization is a change of state from solid to gas without pass- ing through the liquid state, A typical example is dry ice, which can sublimate at rt. and at atmospheric pressure. This technique is used for purification of solids that exhibit exceptionally high vapor pressures and m.p., making these solids transform directly to the gas phase. Other substances are subject to sub- imation, such as iodine, sulfur, naphthalene, ete. This purification technique is suitable for poorly soluble solids and cannot be isolated in a pure state by suc- cessive recrystallizations. Normally, it is performed using vacuum distillation equipment (see Figure 4.18) for very pure yield. Unlike recrystallization, this technique is not commonly to used purify solids. For certain substances, sublimation at atmospheric pressure can be per- formed as follows: © The solid that is to be converted into steam is heated in a beaker.