EXPERIMENT RECRYSTALLIZATION Through the hushed air the whitening shower descends, At first thin-wavering; till at last the flakes Fall broad and wide and fast... . James Thomson, The Seasons: Winter 1 INTRODUCTION Most products from organic reactions are initially not pure, but contain side products, unconsumed reactants, and other impurities which must be removed If the product is a solid and the amounts of the impurities are not very large, the product can frequently be purified by a process called reerystallization, where a hot solution containing the product is slowly cooled, and crystals of the purified product are slowly and selectively precipitated. The proce- dure works because the impurities either remain dissolved in the solvent or are removed before cooling by filtration or adsorption on Norit or decolorizing carbon, Suction filtration then allows the crystals of the purified product to be collected. The general steps for any recrystallization are as follows: 1. Select a proper solvent. 2. Heat the solvent to its boiling point. 3. Dissolve the solid compound in the minimum amount of boiling solvent. 4. Add decolorizing carbon if necessary 5. Filter the hot mixture through a heated, wide-stem or stemless funnel to remove the decolorizing carbon and any insoluble imputities. (This step may be omitted if not applicable.) 79EXPERIMENT 3 6. Allow the hot solution to slowly cool to room temperature or lower. 7. If crystals do not appear, scratch the solution against the flask with a Jass rod, cool the solution further, or add a seed crystal of saved product. 8. Collect the crystals by suction filtration, using a Biichner or Hirsch funnel. 9. Rinse the crystals with a small amount of cold solvent. 10. Dry the crystals. 14. If worthwhile, obtain a second crop of crystals These steps will now be considered in detail 3.2 SELECTING A PROPER SOLVENT The selection of a proper solvent is vitally important in any recrystallization. A lesirable solvent is one in which the product will be very soluble at high tem- yeratures, but only slightly or sparingly soluble at room temperature or lower. This large difference in solubility is crucial for success. If the product is ery soluble in both the hot and cold solvents, too much of it will be lost to he solvent, resulting in a poor yield of purified material. And if the product is ynly somewhat soluble in the hot solvent, then a large quantity of the solvent vill be required and again the amount of product lost to the solvent will be sigh. Figure 3-1 shows a graph of solubility versus temperature for a good sol- rent (line A) and two poor solvents (lines B and C). Observe the steep solubility- fersus-temperature slope for the good solvent, but the moderately increasing opes for the poor solvents ‘The solvents commonly used for a recrystallization are given in Table 3-1 Note that this table now excludes carcinogenic or highly toxic solvents such as senzene, dioxane, chloroform, and carbon tetrachloride, High-boiling solvents uch as dimethyl sulfoxide and N.N-dimethylformamide are also excluded be- -ause of the added difficulty in drying the purified crystals. Although ethyl ether, methylene chloride, and petroleum ether are included n the table, they usually are not as preferred. Their low boiling points generally mean a lower temperature difference between the “hot” and cold solvents, re- ulting in the solute usually not having as large a difference in solubility. In \ddition, their lower boiling points mean a larger solvent loss to vaporization n the decolorizing and filtering steps. The choice of the best possible solvent is often a matter of trial and error. An experienced chemist, though, is usually able to select one after only a few rials. If the product being isolated is not a new one, the chemieal literature most likely will report or recommend the use of certain solvents. For new com- pounds, the general rule “like dissolves like” is valuable. Polar solutes would. hus be more likely to dissolve in polar solvents, such as water and 95", ethanol, AM NHHHANNHANANAANAANAAAHAAHANHAN FE.RECRYSTALLIZATION 81 . A poor solvent. The product is very soluble at all temperstres, A. Agood solvent. The product is vary soluble at higher temperatures, but ont sightly or Sparingly soluole at codm temperature or Solubility B. A poor solvent. The product is only somewhat folubie at nigher temperatures. Temperature —= - FIGURE 3-1 Graph of solubility versus temperature for a good recrystal- lizing solvent and two poor recrystallizing solvents. and less likely to dissolve in nonpolar solvents, such as cyclohexane and ligroin. For nonpolar solutes, the opposite solubility is true. Usually a solute is polar when it is either ionic or when a large portion of the molecule is a functional group, such as —OH, —NH,, —COOH, and -NHCOCH,. Solubility in water and alcohol usually results from the forma- tion of hydrogen bonds between these functional groups and the solvent. For example: ° HoH Ho CH ? ° H { H UH H HO ~C-O-H-. 0% NEU O NC H an “Ht H CHy oO. HO H HEXPERIMENT 3 82 Moy Mor MoT OT uangpayy wumpony cumpapy 01 wnpapy umpoyy xunpoyy mo} £294 uN Aayopxo3 wonerequt uatH uBiy Kay Not wumpoyy iy 29 aut uy wuntpayy snp aU0N mmjoduon. snyoduon, srjoduon, arjoduon, MoT sreypowioiyy sumypoworuy aimipousaiuy airypaweiu, areypauoy uy £304 oa wey A909 Ayejoa 19A10S a}qnjosuy prantosuy arqnjosuy njosuy injosuy 08-09 suoqanaoapu, Jo SUMxI, suoquesosp iy Jo 2umxIy, > "HOOK" "tH "HOFHOFOD'HO oH onto on%HO? Ho'HO HO'HO'HD On emuuos uranjospsyenoy auoraoy fourm our "s6 sea quonjos SwaAjog wonezEISKa99y woUO:) “he seviRECRYSTALLIZATION As the proportion of one of these functional groups in a molecule decreases and the hydrocarbon portion increases, the solute becomes less soluble in polar solvents and more soluble in less polar and nonpolar solvents. In water, for example, acetamide is soluble, but caproamide is only slightly soluble, But in toluene, acetamide is only slightly soluble, whereas caproamide is soluble. e i —C—NH, CH,-(CH,),—C—NH, Acetamide Caproumide Water soluble, Slighily soluble Slightly soluble water, in toluene Soluble in toluene To discover the best solvent for a new compound, place approximately 20 mg (a small spatula-tip full) of the compound in a 10 x 75 mm test tube, Add about 0.5 mL of the possible solvent at room temperature with stirring and note the solubility. If most or all of the compound dissolves, then the solvent is unsatis- factory, since too much of the compound is being lost to the solvent. If only a small part of the compound, however, appears to dissolve, then the solvent may be satisfactory. Place the test tube in a hot-water or steam bath and observe how much of the compound dissolves in the hot or boiling solvent. If the amount is small or moderate, the solvent is again unsatisfactory. But if most or all of the compound dissolves, a good recrystallization solvent has likely been found. If necessary, add a small amount of extra solvent to attain a complete solution, then allow the test tube to slowly cool, and compare the quantity and size of the resulting crystals with the original material. If necessary, induce crystalliza- tion by adding a crystal of the original material to “seed” the cooled solution, The inside of the test tube near the bottom may also be carefully rubbed with a glass stirring rod Sometimes the product being isolated will be too soluble in some solvents and not soluble enough in others. In this case, a mixture of solvents such as the ones in Table 3-2 can be useful. For example, suppose that the product is very soluble in ethanol but not very soluble in water. The product would be dissolved in the minimum amount of hot ethanol, and hot water would then be added slowly until crystallization or turbidity occurred. Hot ethanol would then be TABLE 3-1 Solvent Pairs Methanol-water — Ptherherane Ethanol-water—— Ltherspetroleum ether Acetome-water Methylene ehloride methanol Fiher-methanol — Toluenestigsoin 83EXPERIMENT 3 added slowly until a complete solution was again attained, and the solution would be allowed to slowly cool, When selecting a solvent, be careful to avoid any liquid which could react chemically with the compound being recrystallized. Also avoid any liquid whose boiling point is higher than the melting point of the compound being recrystal- lized. Otherwise, the solid may melt in the solvent and may then “oil out,” This is undesirable because often the oil will be an excellent solvent for impurities, and when the oil finally freezes, the dissolved impurities in the oil will be em. bedded in the crystals. 3.3 DISSOLVING THE SOLID Once a satisfactory recrystallizing solvent has been selected, it is heated to its boiling point in an Erlenmeyer flask and is then slowly added in small por- Hons with stirring to a separate Erlenmeyer flask containing the compound to be recrystallized. Be sure to add only the minimum amount of the boiling solvent needed to dissolve the compound. This ensures that the solution, when cooled, will return the maximum possible yield of product as crystals. Remember that the compound being recrystallized may dissolve only slowly in the boiling solvent, so each extra portion of solvent should not be added too quickly. It is also possible that the compound being recrystallized may contain a few insoluble impurities, and too much solvent may needlessly be added in a futile attempt to dissolve them. Don’t ever perform the reverse process of adding the compound to be recrystallized to the boiling solvent. Otherwise, it may then be im- Possible to tell when the solution is saturated. 3.4 DECOLORIZATION The use of Norit or decolorizing carbon is sometimes successful in removing colored impurities from the product, but if no substantial improvement occurs, the process is not repeated. The fine carbon particles have a large, active surface, which readily attracts and adsorbs many of the resinous, polymeric, and other reactive impurities often found in organic reaction mixtures. The adsorption is not as effective at higher temperatures, but Norit is usually used in the hot liquid in order to keep the product from being recrystallized in solution. The amount of Norit added to the hot liquid should be approximately 2-3 Percent of the weight of the product being recrystallized. Any excess will only adsorb part of the product, resulting in a lower yield. Since the addition of the Norit use the hot mixture to boil over, it is important to cool the mix ture somewhat beforehand, and then reheat to boiling after the addition. The Norit will also cause the mixture to bump. possibly throwing the hot contents dangerously out of the flask. This can be minimized by continuous stirring an AMAaaananaaneaaanenan nae manne eRECRYSTALLIZATION 5 FILTERING THE HOT MIXTURE If any insoluble impurities or decolorizing carbon is present, the hot mixture is next gravity filtered through fluted filter paper in a stemless or wide-stem, heated funnel as shown in Figure 3-2. A stemless or wide-stem funnel avoids the possible problem of clogging inside the stem from premature crystallization. A heated funnel prevents the cooling of the hot mixture during filtration, which may cause premature crystallization in the filter. You can heat the funnel by placing it at the top of an Erlenmeyer flask containing a small amount of boiling solvent. During the filtration into the flask, the hot vapors will rise up around the funnel and heat it. A fluted filter is ordinary filter paper specially folded to provide the maxi- mum possible surface area, This allows the filtration to occur as rapidly as pos- sible. Fluted filter paper can be purchased commercially, or you can easily make it. One way of doing it is shown in Figure 3-3. Itis best to pour the hot mixture through the fluted filter gradually to prevent too large a buildup of solvent in the paper. The mixtures in both flasks should 85 Gravity filtration setup for recrystallization, Hot platemegnetic stirar or staam bathRECRYSTALLIZATION also be kept at the boiling point to prevent premature crystal formation. If too much solvent boils away, it may be necessary to add a small quantity of hot solvent to maintain the volume. Despite the heated funnel, crystals may still sometimes form in the filter during the filtration. If this occurs, a small amount of boiling solvent may be added to redissolve the crystals, This extra amount should be boiled off once the filtration is completed. Remember that this hot filtration process is only necessary if the hot mix- ture contains insoluble impurities or decolorizing carbon. A clear and colorless hot solution with no visible solid material is ready for the next step. 3.6 COOLING AND RECRYSTALLIZATION The Erlenmeyer flask containing the product is now stoppered and set aside, and the hot filtrate is allowed to slowly cool without agitation. Rapid cool- ing and agitation are generally undesirable because the crystal formation will occur too rapidly, resulting in impurities becoming trapped within the crystal lattice. Once room temperature is reached, the flask can be further cooled in an ice-water bath. The lower solubility of the product at this lower temperature will produce a larger yield. Ifthe cooled solute does not crystallize, several techniques can be employed. Further cooling in the ice-water bath may be successful. One can also scratch the solution against the inside of the flask with a glass rod. If a small amount of the original solid material was saved, a crystal of this material may be added to “seed” the cooled solution. Once crystal formation has begun, it is important not to collect the product too early. Otherwise some material may be lost which would have separated from solution with further standing. Patience is a virtue. 3.7 COLLECTING THE CRYSTALS When recrystallization is complete, the product is collected by suction filtration ona Biichner or Hirsch funnel Suction filtration is usually preferred here over gravity filtration, because the difference in pressure increases the rate of liquid flow through the filter. This not only saves time, but reduces the evaporation of the solvent in the funnel, which could redeposit impurities back on the prod- uct. However, suction filtration is usually not used for filtering hot solutions. The reduced pressure in the collecting flask may frequently cause the hot filtrate to boil and the material in solution to be unwantedly deposited everywhere. In addition, clogging of the small holes in the funnel can occur, as well as the bumping and frothing of the filtrate.EXPERIMENT 3 The apparatus for a suction filtration is shown in Figure 3-4, and consists 88 of the funnel in a filter flask connected to a safety trap, which in turn is con- nected to a water aspirator or a “house” vacuum line. Only heavy-walled rubber tubing can be used for the apparatus, because thin-walled tubing will collapse under vacuum from the outside pressure of the atmosphere. If there is no “house” vacuum line, the vacuum in the apparatus is produced by the water aspirator, which consists of a side arm attached to a pipe of changing inner diameter. As the water runs through the pipe, the change in dia- meter changes the speed of the passing water, which, by Bernoulli's principle, creates a partial vacuum in the side arm. A clamped safety trap should always be used with an aspirator. If the | water pressure drops or the water is turned off while the filter flask is under | vacuum, the pressure in the filter flask may be less than the pressure in the aspi- rator. This would cause water to flow from the aspirator into the filter flask and thus contaminate the filtrate, The safety trap stops this reverse flow. The clamp or stopcock on the trap also allows the vacuum to be quickly and easily released. You should always do this before turning off the water, to FIGURE 3.6 Suction filtration apparatus. aspirator or "house" aun fl Heavywalled “bingRECRYSTALLIZATION avoid the backflow of water. The released vacuum also makes it easier to disconnect the filter flask from the trap or the funnel, The filter paper for the Biichner or Hirsch funnel should be just large enough to completely cover the holes while lying flat on the perforated surface. If necessary it should be trimmed so that it does not climb the sides of the fun- nel. Otherwise it may be difficult to create a vacuum in the filter Mask and mate- rial may flow over this loose edge and not be filtered Suction is next applied, and a small quantity of the solvent from which the crystals will be isolated is poured over the paper. After this liquid is filtered through, the paper will cling tightly to the bottom of the funnel so that no smaill particles of the solid can slip under the paper und reach the filtrate below. The crystals can now be collected on the filter paper. Frequently the crystals. will lie on the bottom of the flask, and it is necessary to swirl the liquid. This will temporarily suspend these crystals in the liquid to aid in their transfer while pouring. Any crystals remaining in the flask after all the solvent has been poured may be collected by rinsing with the filtrate collected in the filter flask. Before removing the funnel from the filter flask, remember to release the vacuum by opening the clamp or stopcock on the trap. After all the crystals are collected and no more liquid is visible in the funnel, the crystals should be carefully pressed with a clean cork under continued suc- tion, This will help remove some additional filtrate adhering to the crystals. 3.8 WASHING THE CRYSTALS ‘The isolated crystals in the funnel are now washed with several small quanti- ties of fresh cold solvent. The purpose of this washing is to remove any impurities in the solvent which are on the surfaces of the crystals. These impu- rities would remain on the crystals after the solvent evaporated if they weren't rinsed away. To wash the crystals, open the stopcock or clamp on the trap to release the vacuum, Then break up the crystalline cake with a spatula, being careful not to disturb or break the filter paper. Next add enough fresh cold solvent to just cover the crystals and earefully stir the mixture with a spatula to ensure complete rinsing. Then reclose the stopcock or clamp on the trap, remove as much solvent ats possible by suction filtration, remove any additional adhering solvent by pressing with a clean cork. and repeat the washing process at least one more time. 3.9 DRYING THE CRYSTALS [Alter the erystals have been washed, they must now be thoroughly dried. They should be left in the funnel until the solvent has stopped dripping: they can then be spread out on a large watch glass and left to air dry. Any large chunks which 89EXPERIMENT 3 might entrap the solvent must be broken up, and the final product should either be crystalline or powdered to provide as much surface area as possible. The crystals may be considered dry when there is no further loss of weight and they do not stick to themselves or to the glass. If necessary, you can accelerate the drying process by placing the watch glass in a drying oven. However, a number of problems are possible here. 1. The crystals may melt unless the temperature of the oven is at least 10-20° below the melting point of the crystals. Remember that the melting point of the crystals is lowered by the presence of the solvent. 2. Crystals that sublime easily should not be dried in an oven, since they could disappear by vaporization. 3. Some compounds decompose upon exposure to heat and should therefore not be oven dried. 4. If many students’ samples are being dried in the same oven, the crystals might be lost due to an accident, a mixup in the samples, and so on. Always be sure to clearly label your product. A vacuum desiccator containing a drying agent may also be used to accelerate the drying process, Although there is no danger from heat here, there are other possible problems. 4. Crystals that sublime easily should not be dried in a vacuum desiccator, since the reduced pressure makes vaporization more likely. 2. The vacuum desiccator could possibly implode. It should not be used unless it is placed in a protective cage. 3. The release of the vacuum could blow your product all over the desiccator. Instead of a watch glass, use an Erlenmeyer flask and release the vacuum slowly. 3.10 SECOND CROPS The filtrate in the filter flask contains additional product which frequently can be worthwhile to collect. Do this by boiling off most of the solvent and allowing the concentrated filtrate to cool slowly. The crystals obtained, however, are usually not as pure as those from the first crop. 3.11 LIMITATIONS OF RECRYSTALLIZATION As valuable and useful as recrystallization can be for effectively purifying many solid compounds, one must realize that the method cannot be indiscriminately used for all solid mixtures. {n general, a recrystallization is successful when there }are only smalll amounts of impurities present. With larger amounts of impuri- 91 3.12 EXPERIMENTAL A. Solubility tests Determine the solubility of benzoic acid, sodium benzoate, resorcinol, anthra- cene, and stearic acid in each of the following solvents: water, 95% ethanol, and ligroin. The structure of each of these solutes is given below. 9 ° OH C—on ot O° Nat a om © O1,, COS — Sodium benzoate ne Anthracene 9 . i CHy+tCH ye C—O Steaised To determine the solubility, place about 20 mg (a small spatula-tip full) of each finely crushed solute into a Separate, labeled |() x 75 mm test tube. Unless some test tubes are reused, a total of 15 will be required. Add 0.5 mL. of water, 95% ethanol, or ligroin to the Appropriate test tubes and stir with a Blass rod, being sure the rod is clean in each ease, Neatly record your observa- tions in table form in your notebook, using the following definitions: Soluble: Most or all of the solute dissolved Slightly soluble: A small portion of the solute dissolved. Imsoluble: None of the solute appeared to disolve HT the solute is insoluble or only slightly soluble in the solvent, heat the test tube in a steam bath or a hot-water hath heated by a hot plate and mot by a Bunsen burner; remember the fire huvard, especially with ligroin), Neatly record 'ntable form in your notebook the solubility of the solute ty the hot or boilingEXPERIMENT 2 solvent, using the above definitions. If any of the solutes now dissolve, allow the hot solutions to slowly cool to room temperature and compare the quantity, size, and shape of the resulting crystals with the original material, neatly rec- ording the results in your notebook. From your results, indicate which solvent, if any, you would consider the best one to use for recrystallizing each solute, Also indicate the reason for your decision. What possible alternative solvents or solvent combinations might you try for recrystallizing each solute? In terms of polarity, indicate why these alternatives might likely be successful. Recrystallization of impure benzole acid Place 3.0 grams of impure benzoic acid* in a clean 125-mL Erlenmeyer flask and gradually add boiling hot water (heated on a hot plate) with stirring until no more benzoic acid appears to dissolve. Remember that any sawdust in your sample will not dissolve, so do not needlessly add excess water. No more than about 60 mL should be necessary. Pure benzoic acid is colorless, so if your mixture has color, coo! it slightly and add about 0.1 gram of decolorizing carbon. (BO NOT ADD DECOLOR- IZING CARBON TO A BOILING LIQUID.) Reheat and continuously stir the hot liquid to prevent bumping. Filter the hot mixture through a fluted filter paper, using the technique given in Section 3.5. If the filtered solution still has color, repeat the treatment with decolorizing carbon. Stopper and set aside the Erlenmeyer flask containing the hot, colorless filtrate, and allow the hot filtrate to slowly cool to room tempera ture, undisturbed. When no more crystals appear to form, further cool the flask in an ice-water bath for at least 15 minutes. Collect the crystals by suction filtration, using the procedure given in Sec- tion 3.7, and wash them with two small portions of eold water, using the pro- cedure given in Section 3.8. Allow the crystals to thoroughly air dry on a watch glass and, in the meantime, do the decolorization of brown sugar portion of the experiment (Section 3.12C). Determine the yield and the percentage recovery of the dry crystals, showing the calculation setup in your notebook. Also determine the product's melting point and literature melting point, and record the results in your notebook. When finished, submit the product to your instructor in a clean vial or bottle, clearly labeled with the following information: 4. Your name 2. The experiment number 3. The name of the product and its structure "A micture of 100 grams of benzoic avid, 10 grams of sodium chloride, and perhaps 4 sariable amount of savidust and 02 gram of a dye such as Congo red, 92 ~—_ aa manmn mame nr nmeRECRYSTALLIZATION 4, The melting point or boiling point actually observed 5. The actual yield in grams and the tare of the container . Decolorization of brown sugar Brown sugar is partially refined sucrose, C,3H,30,,, and can be decolorized easily with decolorizing carbon. Dissolve 10 grams of dark brown sugar in 65 mL of water in a 125-mL Erlenmeyer flask. Save 5 mL of the solution for comparison purposes; then pour 15 mL of the remaining solution into each of four labeled 50-mL Erlenmeyer flasks. To two of the flasks, add 0.3 gram each of decolorizing carbon, To the remaining two, add 0.1 gram each of decolorizing carbon. Heat one of the flasks with 0.3 gram of decolorizing carbon and one of the flasks with 0.1 gram of de- colorizing carbon to near the boiling point for two minutes with stirring. Then filter each hot solution through fluted filter paper into separate, labeled 50-mL Erlenmeyer flasks. Also stir the contents of the two unheated flasks for the same amount of time as the two heated ones; then filter the contents through fluted filter paper into separate, labeled 50-mL Erlenmeyer flasks. Compare the ap- pearance of the five solutions, and record the results in your notebook. How have the amount of decolorizing carbon and the heating affected the color? Sugars generally ate quite difficult to crystallize. Therefore, this portion of the experiment will stop here. QUESTIONS 1. During a recrystallization, a yellow solution of a compound was treated with charcoal and the mixture was gravity filtered through fluted paper. When cooled, the crystals obtained were gray, although the compound was known to be colorless. Explain what could account for the gray color of the crystals and what you would do to obtain a colorless product. 2. Explain why washing an impure solid with a cold solvent is not as good as recrystallization for removing all the soluble impurities. 3. What criteria make a solvent satisfactory for a recrystallization? 4. Why are benzene and dimethyl sulfoxide generally not advisable to be used for a recrystallizing solvent? 5. Why is the final product from a recrystallization isolated by suction filtra~ tion rather than gravity filtration? 6. Ifa little decolorizing carbon does a good job in removing the impurities during a recrystallization, why shouldn't you use a lot to do an even better job? 7. Why should decolorizing carbon not be added to a solvent that is at or hear its boiling point? 8. Why is it important to use a safety trap in a vacuum filtration? 9310. iL 12. 13. 14. 15, 16. 17. EXPERIMENT 3 Why is the quality of product obtained from second crops generally not as good as that from first crops? Why isa fluted filter used for hot filtratio: What can cause premature crystal formation, and how can the problem be solved after it has occurred? Ina recrystallization, why does one add the solvent to the solid rather than the solid to the solvent? How can the purity of a recrystallized solid be assessed? Why isn’t suction filtration as preferred as gravity filtration for hot solutions? What is wrong with using a narrow, long-stem funnel in the filtration of a hot solution in a reerystallization? Why is it advisable not to rapidly cool a hot solution during a recrystalliza- tion? Explain why the collected crystals in a recrystallization are washed with* cold solvent rather than warm solvent. 94 el