CHEM243

EXPERIMENT 2

RECRYSTALLIZATION

Theory

One of the most necessary and useful techniques to be mastered by an organic chemist is

recrystallization. A compound that is solid at room temperature is usually isolated and

purified by this method. It owes its wide applicability to the tendency of a crystal lattice to

accept only molecules of the right size, shape and bonding forces, hence usually of only a

signal species. This process utilizes the general principle that a solid becomes less soluble in a

solvent as the temperature decreases. Ideally, the entire desired product separates in a

beautifully crystalline form and all of the soluble impurities remain in solution (dissolved in

the mother liquor or supernatant solution).

The steps in purification by crystallization are normally the following:

1. Dissolving the substance in the solvent at boiling point.

2. Filtering the hot solution to remove insoluble impurities.

3. Allowing the hot solution cool and deposit crystals of the substance.

4. Separating the crystals from the mother liquor by filtration.

5. Washing the crystals to remove adhering mother liquor.

6. Drying the crystals to remove last traces of solvent.

The selection of suitable solvent for crystallization is of great practical importance. A good

solvent for this purpose would have the following properties:

1. Chemical inertness to the solute.

3. Sparing solubility of the solute at low temperature.

4. Ease of removal from the isolated crystalline product, preferably by evaporation.

5. Either no solubility of impurities at high temperature or very high solubility of the

impurities at low temperatures.

6. Low cost.

7. Low hazard (flammability, toxicity etc.)

Steps and techniques in crystallization:

i. Preparation of the solution. As a rule, the objective is to dissolve the solute in a minimum

amount of solvent at the boiling point. The following procedure is recommended; place the

finely divided material in an Erlenmeyer flask or suitable size. Add a boiling chip and cover

the solid with previously selected solvent. Warm to boiling on a steam bath (or for high

boiling solvents on a hot plate), constantly stirring the mixture by swirling the flask. Add

more solvent to the boiling solution in small portions with stirring. Allow sufficient time

between additions to give the solute a chance to dissolve. Continue the addition of solvent

until all the solute has dissolved at the boiling temperature.

ii. Decolorizing – frequently the solution is colored by high molecular weight organic

impurities which may be formed as decomposition products or by-products in a synthetic

process. Boiling for one or two minutes with a small amount of an effective absorbent such as

activated charcoal will usually remove the color. The amount of charcoal should be kept to a

minimum for some of the desired product is also absorbed. It has frequently been observed

that charcoal is considerably more effective in solvents which are associated.

the solute crystallize on the filter paper or in the funnel. This usually requires rapid filtration

with a minimum of evaporation through a previously warmed funnel fitted with a fluted filter

paper (see Figure 1).

used, which may be removed by concentration of the filtrate to the volume originally required

dissolving the material.

iv. Cooling the aim of the cooling process is to bring about the crystallization of the maximum

amount of desired material with a minimum amount of impurity. The process should be

carried out in an Erlenmeyer flask covered with a watch glass in order to avoid evaporation.

The hot filtration is allowed to cool slowly by standing at room temperature. Rapid cooling by

immersion in water, etc. is undesirable because the crystals formed will tend to be quite small.

Their large surface area may then facilitate adsorption of impurities from the solution.

Generally the solution should not be agitated while cooling, since this will also lead to the

formation of small crystals. However, formation of very large crystals (larger than

approximately 2 mm) may cause occlusion (trapping) of solution within the crystals. Such

crystals are difficult to dry and will, when dried, have deposits of impurities in them. If large

crystals seem to be forming, agitation may be used to lower the average crystal size. If

crystallization does not occur after cooling, the super-saturated solution can usually be made

to yield crystals by seeding. A tiny crystal of the original solid is added to the cooled solution.

Crystals will usually form quite rapidly. Another method that may be used to induce crystal

formation is to scratch the inside surface of the flask at or just above the surface of the

solution with a glass rod.

Occasionally the solute will separate as oil rather than as crystals from the solution. This

occurs when the limit of solubility of the solute is reached on cooling at a temperature that is

above the melting point of the substance. This can usually be avoided by diluting the solution

with more solvent, reheating and again allowing cooling. Sometimes choice of a different

solvent is necessary.
v. Collecting the crystals: The major aim here is the removal of a maximum amount of mother

liquor from the crystals. This is usually accomplished with a Buchner funnel fitted by means

of a rubber stopper into a clean filter flask connected through a safety bottle (or trap) to a

water pump (Figure 2). The smallest funnel which will accommodate all of the crystals

comfortably with no danger of overflow should be used. For small samples, a Hirsch funnel is

recommended.

The filter paper should cover the entire perforated area of the plate. It should be flat so that no

solid material can pass under its edge. This is accomplished by wetting the paper with solvent

and applying suction. Use of a glass or spatula will make possible the rapid transfer of the

bulk of crystals to the funnel. The lost quantity of the crystals may be transferred by washing

them out of the flask with some of the mother liquor.

The crystal should be passed down carefully but family by means of a cork. They should then

be washed by releasing the pressure and just covering the crystals with cold fresh solvent.

After a few seconds, the solvent is removed by suction. The purpose of this washing step is to
remove the solution with which the crystals are wet. This must be done for successful

purification; the solution, obviously, contains the soluble impurities.

Before removing the funnel from the filter flask release the pressure by opening the screw

clamp or stopcocks on the trap.

vi. Drying the crystals: most of the solvent may be evaporated by allowing the aspirator to

pull air through the mass of crystals on the funnel for a few minutes. By means of a spatula,

the crystals are then transferred to a clean watch glass. Complete drying is accomplished by

allowing them to air-dry for a few hours or (faster) by placing the watch glass in an oven. In

drying solids above room temperature one must take into account that samples that are still

moist with solvent melt considerably below the melting point of the pure material, (Why?).

Solvent selection:

If the compound has been previously studied, consultation of the chemical literature will

generally give information concerning a suitable solvent. If not, it will be necessary to resort

to trial and error methods using small amount of material. Some general solubility principles

should be kept in mind if this needs to be done. Normally polar compounds are insoluble in

nonpolar solvents and soluble in polar solvents. These solubility relationships are frequently

summarized with the phrase “like dissolves like”. Compounds in which polar groups

(particularly –OH, -NH2 , -COOH, or –C(O)NH2 , which can form hydrogen bonds) comprise a

major part of the molecule are usually more soluble in hydroxylic solvents such as water or

alcohols.

Non-polar and compounds of intermediate polarity i.e. compounds in which the effect of polar

functional groups are supersede by the hydrocarbon (non-polar) part of the molecule, dissolve

in common organic solvents like ether, chloroform, acetone, ethyl acetate, benzene. Non-polar
compounds, which lack hetero atoms (N, S, O and P) are usually soluble in non-polar liquids

as pentane, hexane, petroleum ether, ligroin, cyclohexane and carbontetrachloride.

Occasionally a mixture of two solvents (solvent-pair) is more satisfactory then a signal

solvent. Such solvent-pairs are made up of two mutually soluble liquids, one of which

dissolves the substance readily and another which dissolve it very sparingly. Examples of

solvent pairs are ethanol and water, diethyl ether and petroleum ether, ethyl acetate and

benzene.

The crystals are first dissolve in boiling solvent in which they are soluble. The second solvent

is then added to the boiling solution until the solution turns cloudy. Then just enough of the

first solvent is added to clear the turbidity, and the solution is allowed to cool in the usual

manner. The second solvent decreases the dissolving ability of the solvent medium; When the

solubility limit is reached, the solute begins to come out of solution in a cloudy appearance.

Experimental Procedure:

Selection of a crystalizing solvent:

Make the solubility tests on each of the compounds given (naphthalene, benzoic acid and

acetanilide) in each of the following solvents: water, ethyl alcohol, acetone, benzene.

Observe and record the degree of solubility in each solvent, hot and cold, select the best

solvent pair for each of the substance (!). Record the general crystalline from-needles or

prisms, spheres; platelets carry out the solubility tests as follows:

- With a small spatula, transfer an amount, roughly estimated to be 0.1g, of the finely

divided solid to a small test tube and add the solvent drop by drop with continuous

shaking. Stir with a stirring rod. After 1 mL of the solvent has been added observe the

mixture carefully.
NOTE: some solvents tend to evaporate easily from the test tube so add the solvent, if

necessary, to maintain the same amount of solvent for comparison.

- If all the solid has dissolved in the cold solvent, the solvent is unsuitable (we

mentioned it before: finding a good solvent).

- If not all the solid has dissolved, warm the mixture gently to the boiling point with

stirring. If all the solid dissolves, you can declare it readily soluble in hot solvent (you

are very lucky). If not all dissolves, add more solvent in 0.5 mL portions until all of

the solid dissolves at the boiling point or until a total of 3 mL of solvent is present. If

some of the solid still remains undissolved at the boiling point, you can judge it

sparingly soluble in that solvent and you should try another crystallizing solvent. If all

of the solid does dissolve in a total of less than 3 mL of the hot solvent you can declare

the material at least moderately soluble in that solvent.

- In very case, when a solution of solid in a hot solvent is obtained, slowly cool the

solution, scratching the sides of the test tube with a small stirring rod. Observe the

ease and amount of crystal formation. Note and record the approximate proportions of

solute and solvent which give the best results. On this basis, select the most suitable

crystallization solvent for each substance. If no single solvent appears to be

particularly suitable, try mixed solvents.

NOTE: Do not disturb the solution. Slow cooling gives the best crystals.

- Recrystallize an unknown sample given to you, in a solvent which you choose by

applying same tests as above

NOTE: If no crystallization occurs after the solution has cooled, it indicates either too

much solvent has been used or that the solution is supersaturated. The crystallization
can be induced by adding a crystal of the original solid in super saturated solution. If no

solid is available and a volatile solvent is being used, immerse the tip of a glass rod or

metal spatula in the solution for a few seconds. The crystals that form at the end of the

rod or spatula are then added into the solution to initiate crystallization.