| Crystallization | |
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| Concepts | |
| Crystallization · Crystal growth Fractional crystallization Recrystallization · Seed crystal Single crystal |
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| Fundamentals | |
| Nucleation · Crystal Crystal structure · Solid |
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Recrystallization is a physical process.
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In chemistry, recrystallization[1] is a procedure for purifying compounds. The most typical situation is that a desired "compound A" is contaminated by a small amount of "impurity B". There are various methods of purification that may be attempted (see Separation process), which includes recrystallization. There are also different recrystallization techniques that can be used such as:
Typically, the mixture of "compound A" and "impurity B" are dissolved in the smallest amount of hot solvent to fully dissolve the mixture, thus making a saturated solution. The solution is then allowed to cool. As the solution cools the solubility of compounds in solution drops. This results in the desired compound dropping (recrystallizing) from solution. The slower the rate of cooling, the bigger the crystals formed.
In an ideal situation the solubility product of the impurity, B, is not exceeded at any temperature. In that case the solid crystals will consist of pure A and all the impurity will remain in solution. The solid crystals are collected by filtration and the filtrate is discarded. If the solubility product of the impurity is exceeded, some of the impurity will co-precipitate. However, because of the relatively low concentration of the impurity, its concentration in the precipitated crystals will be less than its concentration in the original solid. Repeated recrystallization will result in an ever purer crystalline precipitate. The purity is checked after each recrystallization by measuring the melting point, since impurities lower the melting point. NMR spectroscopy can also be used to check the level of impurity. Repeated recrystallization results in some loss of material because of the finite solubility of compound A.
The crystallization process requires an initiation step, such as the addition of a "seed" crystal. In the laboratory a minuscule fragment of glass, produced by scratching the side of the glass recrystallization vessel, may provide the nucleus on which crystals may grow. Successful recrystallization depends on finding the right solvent. This is usually a combination of prediction/experience and trial/error. The compounds must be more soluble at the higher temperature than at the lower temperatures. Any insoluble impurity is removed by the technique of hot filtration.
This method is the same as the above but where two (or more) solvents are used. This relies on both "compound A" and "impurity B" being soluble in a first solvent. A second solvent is slowly added. Either "compound A" or "impurity B" will be insoluble in this solvent and precipitate, whilst the other of "compound A"/"impurity B" will remain in solution. Thus the proportion of first and second solvents is critical. Typically the second solvent is added slowly until one of the compounds begins to crystallize from solution and then the solution is cooled. Heating is not required for this technique but can be used.
The reverse of this method can be used where a mixture of solvent dissolves both A and B. One of the solvents is then removed by distillation or by an applied vacuum. This results in a change in the proportions of solvent causing either "compound A" or "impurity B" to precipitate.
Hot filtration[2] can be used to separate "compound A" from both "impurity B" and some "insoluble matter C". This technique normally uses a single-solvent system as described above. When both "compound A" and "impurity B" are dissolved in the minimum amount of hot solvent, the solution is filtered to remove "insoluble matter C". This matter may be anything from a third impurity compound to fragments of broken glass. For a successful procedure, one must ensure that the filtration apparatus is hot in order to stop the dissolved compounds crystallizing from solution during filtration, thus forming crystals on the filter paper or funnel.
One way to achieve this is to heat a conical flask containing a small amount of clean solvent on a hot plate. A filter funnel is rested on the mouth, and hot solvent vapors keep the stem warm. Jacketed filter funnels may also be used. The filter paper is preferably fluted, rather than folded into a quarter; this allows quicker filtration, thus less opportunity for the desired compound to cool and crystallize from the solution.
Often it is simpler to do the filtration and recrystallization as two independent and separate steps. That is dissolve "compound A" and "impurity B" in a suitable solvent at room temperature, filter (to remove insoluble compound/glass), remove the solvent and then recrystallize using any of the methods listed above.
Crystallization requires an initiation step. This can be spontaneous or can be done by adding a small amount of the pure compound (a seed crystal)[1] to the saturated solution, or can be done by simply scratching the glass surface to create a seeding surface for crystal growth. It is thought that even dust particles can act as simple seeds.
Growing crystals for X-ray crystallography can be quite difficult. For X-ray analysis, single perfect crystals are required. Typically a small amount (5–100 mg) of pure compound is used, and crystals are allowed to grow very slowly. Several techniques can be used to grow these perfect crystals:
For ice, recrystallization refers to the growth of larger crystals at the expense of smaller ones. Some biological antifreeze proteins have been shown to inhibit this process, and the effect may be relevant in freezing-tolerant organisms.
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