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Recrystallization (chemistry)

physical science Maturity 9-11 Next article →

Recrystallization is a broad class of chemical purification techniques. Scientists use it to separate a pure substance from an impure sample. This process involves dissolving an impure sample in a solvent or a solvent mixture. After dissolving the sample, the scientist changes the conditions to encourage the formation of pure solid crystals. This method is essential because crystallized compounds are extremely important in many scientific fields.

Single Solvent Recrystallization
Single Solvent Recrystallization

The mechanism of purification relies on spontaneous processes of self-assembly. Crystals possess a highly ordered, periodic molecular structure known as a crystal lattice. This low-entropy structure is the driving force behind the purification. The process works because of different molecular interactions between the desired isolate and the impurities. If a molecule of the desired isolate interacts with an existing crystal, it likely deposits on the ordered surface. This contributes to the growth of the crystal. However, if an impurity molecule interacts with the crystal, it is unlikely to deposit on the ordered surface. Consequently, the impurity remains dissolved in the solvent.

Mixed Solvent Recrystallization
Mixed Solvent Recrystallization

Initial crystals of the isolate form through processes of stochastic nucleation. These tiny starting points grow into macroscopic sizes as isolate molecules deposit on them. One common method is temperature manipulation. This is used when the isolate has an endothermic dissolution, meaning it requires heat to dissolve. In this case, the solubility product, or Ksp, increases as the temperature rises. A scientist prepares a saturated solution of the impure sample near the boiling point of the solvent. The sample may start as a solid powder or a viscous liquid. The solution is then slowly cooled to create a supersaturated solution. This state makes crystal nucleation imminent.

Hot Filtration Recrystallization
Hot Filtration Recrystallization

There are several distinct methods used to achieve crystallization. Slow evaporation is a popular technique where a solid is dissolved in a single solvent. The solvent is then allowed to evaporate slowly until the solution becomes saturated. Another method uses a multi-solvent system. In this case, the composition of the solvent changes as the more volatile solvent evaporates. This makes the compound increasingly insoluble, causing it to crystallize.

x-ray crystals - slow evaporation 2 solvent
x-ray crystals - slow evaporation 2 solvent

Scientists also use mixed solvent systems, such as aqueous ethanol, to aid the process.

Another method involves the use of an antisolvent. This requires the product to be much more soluble in the primary solvent than in a second solvent. The two solvents must be miscible, meaning they can mix together. The scientist adds the antisolvent to the solution until incipient precipitation occurs. The volume ratio between the two solvents and the concentration of the sample are both important factors.

Mixed Solvent Recrystallization
Mixed Solvent Recrystallization

Some scientists prefer to layer the antisolvent on top of the solution rather than mixing it directly.

Diffusion methods are used to create very specific conditions for crystal growth. In gas diffusion, a second solvent evaporates from one container into a container holding the compound solution. As the solvent composition changes due to the infused vapor, the compound becomes insoluble and crystallizes.

x-ray crystals - slow gas diffusion 2 solvent
x-ray crystals - slow gas diffusion 2 solvent

Liquid-liquid diffusion is another option. Here, two solvents are layered carefully so they do not mix immediately. They diffuse slowly at the interface, which is the boundary where the two liquids meet.

x-ray crystals - slow liquid diffusion
x-ray crystals - slow liquid diffusion

To slow this mixing even further, scientists may use an "H" shaped tool. This tool uses a fine glass sinter to restrict the mixing of the two solvent chambers.

x-ray crystals - slow liquid diffusion - H Tube
x-ray crystals - slow liquid diffusion - H Tube

Once the crystals are obtained, they are often studied using X-ray crystallography. This technique is used to assess the purity of the product. For this to work, the crystals must be singular and absent of clumps. It is also vital to store the crystals in a sealed vessel with some of the liquid of crystallization. Single perfect crystals can contain solvent within their crystal lattice. If this internal solvent is lost, the lattice may break down. This causes the crystals to turn into a fine powder.

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🖼️ Images & Media (8)
File:Single_Solvent_Recrystallization.png
Single_Solvent_Recrystallization.png
File:Mixed_Solvent_Recrystallization.png
Mixed_Solvent_Recrystallization.png
File:Hot_Filtration_Recrystallization.png
Hot_Filtration_Recrystallization.png
File:x-ray crystals - slow evaporation 1 solvent.png
x-ray crystals - slow evaporation 1 solvent.png
File:x-ray crystals - slow evaporation 2 solvent.png
x-ray crystals - slow evaporation 2 solvent.png
File:x-ray crystals - slow gas diffusion 2 solvent.png
x-ray crystals - slow gas diffusion 2 solvent.png
File:x-ray crystals - slow liquid diffusion.png
x-ray crystals - slow liquid diffusion.png
File:x-ray crystals - slow liquid diffusion - H Tube.png
x-ray crystals - slow liquid diffusion -...
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