Crystallization

A. Definition
-is the (natural or artificial) process of formation of solid crystals precipitating from a solution, melt or more rarely deposited directly from a gas. -is also a chemical solidliquid separation technique, in which mass transfer of a solute from the liquid solution to a pure solid crystalline phase occurs. -refers to the formation of solid crystals from a homogenous solution. It is essentially a solid- liquid separation technique and a very important one at that.

B. Process
1. Nucleation
- is the step where the solute molecules dispersed in the solvent start to gather into clusters, on the nanometer scale (elevating solute concentration in a small region), that become stable under the current operating conditions. These stable clusters constitute the nuclei. However, when the clusters are not stable, they re dissolve. Therefore, the clusters need to reach a critical size in order to become stable nuclei. Such critical size is dictated by the operating conditions (temperature, supersaturation, etc.). It is at the stage of nucleation that the atoms arrange in a defined and periodic manner that defines the crystal structure note that "crystal structure" is a special term that refers to the relative arrangement of the atoms, not the macroscopic properties of the crystal (size and shape), although those are a result of the internal crystal structure.

2. Crystal Growth
-is the subsequent growth of the nuclei that succeed in achieving the critical cluster size. Nucleation and growth continue to occur simultaneously while the supersaturation exists. Supersaturation is the driving force of the crystallization; hence the rate of nucleation and growth is driven by the existing supersaturation in the solution. Depending upon the conditions, either nucleation or growth may be predominant over the other, and as a result, crystals with different sizes and shapes are obtained (control of crystal size and shape constitutes one of the main challenges in industrial manufacturing, such as for pharmaceuticals). Once the super saturation

is exhausted, the solidliquid system reaches equilibrium and the crystallization is complete, unless the operating conditions are modified from equilibrium so as to supersaturate the solution again. Many compounds have the ability to crystallize with different crystal structures, a phenomenon called polymorphism. Each polymorph is in fact a different thermodynamic solid state and crystal polymorphs of the same compound exhibit different physical properties, such as dissolution rate, shape (angles between facets and facet growth rates), melting point, etc. For this reason, polymorphism is of major importance in industrial manufacture of crystalline products.

C. Illustration

EXTRACTION
A. Definition
-is a separation technique based on differences in solubilities of substances in two immiscible solvents (usually water and a water insoluble organic solvent). Liquid-liquid extractions using a separatory funnel are essentially the only kind of extraction performed in the organic teaching labs. Liquid-liquid means that two liquids are used in the extraction procedure. The liquids must be immiscible: this means that they will form two layers when added together, like oil and water. Some compounds are more soluble in the organic layer (the "oil") and some compounds are more soluble in the aqueous layer (the "water").

The photo above illustrates how two liquid layers separate. The red layer is simply red food coloring in water. Water is immiscible with the other liquid, which is methylene chloride. Methylene chloride is heavier (denser) than water, therefore, the clear methylene chloride layer is under the red, aqueous food coloring layer.

How to do an Extraction
Support the separatory funnel in a ring clamp on a ringstand. Ring clamps come in many sizes. If yours is too large, you can add pieces of cut tygon tubing to the ring to cushion the funnel, or wrap the ring with tape until it is thick enough to hold the separatory funnel. Make sure the stopcock of the separatory funnel is closed.

Place a stemmed funnel in the neck of the separatory funnel. Add the liquid to be extracted, then add the extraction solvent. The total volume in the separatory funnel should not be greater than three-quarters of the funnel volume.

Insert the stopper in the neck of the separatory funnel.

Pick up the separatory funnel with the stopper in place and the stopcock closed, and rock it once gently.

Point the stem up and slowly open the stopcock to release excess pressure. Close the stopcock. Repeat this procedure until only a small amount of pressure is released when it is vented.

Shake the funnel vigorously for a few seconds. Release the pressure, then again shake vigorously. About 30 sec total vigorous shaking is usually sufficient to allow solutes to come to equilibrium between the two solvents. Vent frequently to prevent pressure buildup, which can cause the stopcock and perhaps hazardous chemicals from blowing out. Take special care when washing acidic solutions with bicarbonate or carbonate since this produces a large volume of CO2 gas.

Put the funnel back into the ring and let it rest undisturbed until the layers are clearly separated. While waiting, remove the stopper and place a beaker or flask under the sep funnel.

Carefully open the stopcock and allow the lower layer to drain into the flask. Drain just to the point that the upper liquid barely reaches the stopcock.

If the upper layer is to be removed from the funnel, remove it by pouring it out of the top of the funnel. Often you will need to do repeat extractions with fresh solvent. You can leave the upper layer in the separatory funnel if this layer contains the compound of interest. If the compound of interest is in the lower layer, the upper layer must be removed from the separatory funnel and replaced with the drained-off lower layer, to which fresh solvent is then added. When you are finished, remember to store the stopper separately from the funnel.

DISTILLATION

A. Definition
-is a method of separating mixtures based on differences in volatilities of components in a boiling liquid mixture. -is a unit operation, or a physical separation process, and not a chemical reaction. -is the process used to purify or separate different components of a mixture.

B. Types of Distillation
1. Simple Distillation

Simple distillation separates liquids based on their differences in boiling point. It's used when there's at least fifty degrees difference in the boiling points of the substances involved. As the distilling liquid is heated, vapors form. The vapors contain components of the substance that boils at the lowest temperature. As distillation continues, the concentration of the lowest boiling substance slowly decreases. Components from the substance with the next-lowest-boiling point start to appear. When the temperature stabilizes, pure distillate from the second substance can be collected. This process can be repeated until the original mixture has been completely separated. Simple distillation is also used to separate volatile and non-volatile substances. 2. Fractional Distillation Fractional distillation is used when a mixture contains liquids whose boiling points are similar to each other. This type of distillation uses a piece of apparatus called a fractionating column. The liquid is heated, and the vapors created rise up the fractionating column. When they reach certain points, they cool and condense. The remaining vapor continues to rise up the column until the next compound condenses. When the vapor reaches the top of the column, the liquid is completely purified. 3. Steam Distillation Normally, a very high temperature is needed to distill organic compounds. Such high temperatures cause these compounds to decompose. Steam distillation can be used to successfully distill these compounds because organic compounds like oils, waxes, and compound fats don't mix with water and will boil well below their boiling points when they're in its presence. For instance, the essential oil eugenol boils at 254 degrees Centigrade and would decompose if it were distilled at that temperature. However, by distilling it with water, it can be distilled at water's boiling point, which is just over 98 degrees Centigrade. Steam distillation is used to extract eucalyptus oil from eucalyptus and to extract oils used in perfumes from different plants. 4. Molecular Distillation Molecular distillation is also known as short-path distillation and is a useful way to purify compounds that don't tend to vaporize and are sensitive to heat. By using a device called a centrifugal evaporator, it's possible to limit the time a compound is exposed to very hot temperatures to just one second. Distillation occurs at low pressure and high vacuum. Molecular distillation is used to make vitamin A esters and mono and diglycerides of fatty acids that are used in baking. 5. Vacuum Distillation Vacuum distillation is a special method of separating compounds at pressure lower than the standard atmospheric pressure. Under this condition, the compounds boil below their normal boiling temperature. Hence, vacuum distillation is best suited for separation of compounds with higher boiling points (more than 200C), which tend to decompose at their boiling temperature. Vacuum distillation can be conducted without heating the mixture, as usually followed in other distillation types. For the separation of some aromatic compounds, vacuum distillation is used along with steam distillation. 6. Short Path Distillation

Thermal sensitive compounds can also separate by following short path distillation. In this technique, the separated compounds are condensed immediately without travelling the condenser. The condenser is configured in a vertical manner between the heating flask and the collecting flask. Similar to vacuum type, the pressure is maintained below the atmospheric pressure. Short path distillation is used for the separation of organic compounds with high molecular weight, especially in the pharmaceutical industries.

C. Uses of Distillation
1. Produces alcohol 2. Making gasoline from oil 3. Manufacturing perfumes and turpentine 4. Converting seawater into drinking water 5. Making vitamins and other nutritional supplements like fish oils 6. To extract essential oils from plants

D. Illustration

UNIVERSIDAD DE ZAMBOANGA PAGADIAN CITY

ASSIGNMENT IN CHEMISTRY LABORATORY

Submitted by: Samina C. Manas Student I-A

Submitted to: Abigail Cabrales Instructor