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Recrystallization
A purification Technique for Solids Objectives To understand the concept behind recrystallization and its usefulness in organic synthesis. Learn how to choose the correct solvent for recrystallization. Introduction Crystallization may be defined as the process in which a solid compound precipitates from a saturated solution in the form of crystals. Saturation is usually effected through cooling or evaporation. - urification by recrystallization depends on the following facts! ". #ifferent solids have different solubilities in a given solvent. $. %ost solids are more soluble in hot than in cold solvents.
Figure 1! a crystallized compound

&hen the impure solid is dissolved in a minimum volume of a suitable hot solvent and the resulting solution is gradually cooled' saturation and eventual crystallization of the pure compound occurs. (mpurities in a solid are of two )inds! soluble and insoluble and recrystallization involves the removal of both to purify a solid. (nsoluble impurities are first removed by gravity filtration of the hot solution while the soluble impurities remain dissolved in the cold saturated solution *mother liquor+ after precipitation of the desired compound. The pure crystals are separated from the supernatant liquid by suction filtration. Generalized Experimental Procedure ,ecrystallization involves the following sequence of steps! ". Selection of a suitable solvent. $. reparation of the solution. -. .ot /iltration *0ravity /iltration+. 1. 2ooling. 3. 2ollecting and #rying of 2rystals.

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4ach step will now be discussed more fully. 1! "election of a suitable solvent A suitable solvent for recrystallization should possess the following important properties! ". #issolve a large amount of the solid to be purified at high temperature. $. #issolve impurities readily at low temperatures *5 soluble impurities+ or not at all even at the boiling point *5 insoluble impurities+. 46perimentally! the suitable solvent is determined through solubility tests. This is done by sha)ing about 7." g of the powdered solid with 8$ mL of the given solvent in a dry test tube. (f the entire solid has nearly dissolved in the cold solvent' the solvent considered unsuitable. (f not' the mi6ture is heated gently to the boiling point with stirring. (f most of the solid did not dissolve' the solvent is also unsuitable. (f a substance is found to be too soluble in one solvent and insoluble in another' then a mi6ture of both solvents *solvent pair+ may be used. (n such cases' the solvents must be completely miscible. The compound to be recrystallized is dissolved in the solvent in which it is very soluble and then the other solvent is added gradually at the boiling point until a slight turbidity occurs. The solution is then allowed to stand at room temperature to effect slow crystallization before chilling in ice. Table "! 2ommon solvents for ,ecrystallization "olvent &ater %ethanol 4thanol Acetone 2hloroform 2yclohe6an e 4thyl acetate &! Preparation of t'e solution To prepare the hot solution' the finely divided solid is placed in an 4rlenmeyer *conical+ flas) and the selected solvent is added in small portions. The mi6ture is stirred and heated to boiling after each addition' until the solid dissolves completely. A slight e6cess of the b!p!# $% "77 93 :; 39 9" ;" :; Particulars of "olvents To be used whenever suitable /lammable' to6ic /lammable /lammable <on-flammable' vapor to6ic /lammable /lammable

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solvent is usually added to compensate for any losses *through evaporation+ during hot filtration. (O)E! #ecolorizing charcoal may added at this stage if the solution is colored due to colored impurities. The flas) should be removed from the heat source before adding charcoal to it' otherwise bumping will occur. *! +ot Filtration ,Gravity Filtration/iltration of the hot solution is necessary to remove insoluble impurities. =pon addition to the funnel' the solution will cool rapidly and this can cause unwanted precipitation. This can be minimized' or avoided' by using a fluted filter paper and a stemless funnel placed on top of a bea)er on a hotplate containing a few milliliters of the recrystallization solvent. .! %ooling 2ooling the filtered solution will allow crystals to form. The rate of cooling plays a role in determining the size of the crystals that form! fast cooling will tend to generate more crystals of small size' slow cooling can allow largest crystals to form. The best compromise of speed' convenience' and crystal quality' is simply to let the solution cool to room temperature on the lab bench. To ensure ma6imum recovery of material' the solution should be cooled in an ice-water bath after the solution has reached room temperature. (O)E! Scratching of the inner surface of the glass can help in crystal formation. /! %ollecting and 0rying of %rystals &hen the crystallization is complete' the crystals need to be collected by suction filtration using a >uchner funnel to ensure rapid and complete removal of the solvent. Transfer the crystalline material as a suspension to the filter' being careful to never fill the funnel over half full. %ost of the time' it will be difficult to completely transfer all of the crystals to the funnel' quantitatively' so it will be necessary to add a small amount of ice-cold solvent to the flas) to help facilitate the transfer of all of the crystals. The crystals are then washed with a little more ice-cold solvent to remove any final impurities that may remain on the surface of the crystals. This solvent should be as cold as possible to )eep the crystals from redissolving. The crystals are finally dried in an oven or allowed to air-dry' in case the melting point is low' by spreading them over a sheet of paper.

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Experimental ? "election of "olvent erform solubility tests on anthracene' salicylic acid' benzoic acid' and sodium benzoate in water' alcohol' and ligroin as follows! &ith a spatula ta)e about 7." g of the powdered solid and place in a dry test tube. Start by dissolving it in about $ mL of solvent with stirring. (f insoluble' heat the mi6ture to boiling *in water bath+ and observe the solubility. The results should allow the selection of a suitable solvent for each compound. ? Recrystallization of an impure un1no2n &eigh about " g of the impure un)nown and recrystallize it from the solvent you have selected.*>y ma)ing a solubility tests on pure un)nown to choose the suitable solvent+. %a)e sure you use the minimum volume of solvent@ otherwise the amount of recovered product will be small. #etermine the weight and melting point of the purified compound.

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Recrystallization
,eport Sheet ? "election of Recrystallization "olvent %ompound Sodium benzoate Salicylic acid Anthracene 6enzoic 4cid ? Recrystallization of an Impure un1no2n -=n)nown letter! - Suitable recrystallizing solvent! - %ass of crude sample! - %ass of purified sample! - A yield! - %elting point of crude sample! - %elting point of pure sample! 3ater %old +ot "olubility 4lco'ol %old +ot

---------------------!<ame

5igroin %old +ot

"uitable "olvent

-&hat is the effect of the presence of impurities on the m.pB -#id you find insoluble impurities in the crude un)nownB .ow can you remove itB

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? 7uestions ". &hat is the purpose of recrystallizationB

$. &hat properties should ideally be possessed by a recrystallization solventB

-. .ow might the melting point of a material differ before and after recrystallizationB

1. &hy should the crystals be washed with e6tra solvent when collected using suction filtrationB &hy cold solventB

3. &hy it is preferable to allow the hot solution to cool gradually instead of chilling immediately in an ice-bathB

9. /or what purpose is charcoal used in recrystallizationB

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:. ,esults of solubility tests for compound A are shown in the following table *gCmL+. &hich solvent will you choose for recrystallizationB Solvent 2old .ot &ater $7 -7 4thanol $3 #iethyl ether 3 3

DDDDDDDDDDDDDDDDDDDDDDDDDDD
Procedure for %rystallization
The photos below illustrate the process of crystallization.

.eat some solvent to boiling. lace the solid to be recrystallized in an 4rlenmeyer flas).

our a small amount of the hot solvent into the flas) containing the solid.

Swirl the flas) to dissolve the solid.

lace the flas) on the steam bath to )eep the solution warm.

(f the solid is still not dissolved' add a tiny amount more solvent and swirl again.

&hen the solid is all in solution' set it on the bench top. #o not disturb itE

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After a while' crystals should appear in the flas).

Fou can now place the flas) in an ice bath to finish the crystallization process.

Fou are now ready to filter the solution to isolate the crystals. lease see the section on vacuum filtration. After your crystals are filtered from the solution' put them on a watch glass as shown below.

.ere is the filter paper with crystals on it.

2arefully scrape the crystals onto the watch glass.

Let the crystal finish drying on the watch glass.

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