Sublimation is a process used to isolate a natural product from other undesired compounds, and then purify it by a direct phase

change of that product from a solid to a vapor, that is, no intermediate appearance of a liquid state is observable. In this process, a solid is heated in a flask or container under vacuum. This method of heating usually makes the solid sublime directly into a gas without first melting into a liquid. The gas is then condensed on a cold surface, which causes the solid to re-form. Impurities, which are usually of heavier molecular weight and do not evaporate as easily, are left behind on the bottom of the container used. Thus, sublimation is usually employed by chemists as a purification method and is particularly valuable for the isolation of a volatile solid from such colored gums and tars.

Many compounds readily sublime including some ketones, amino acids, carboxylic acids, iodine, naphthalene, salicylic acid, camphor and most acid anhydrides and quinones. Crude caffeine (caffeine tetrahydrate) on the other hand, obtained from the previous caffeine isolation experiment, loses its water of hydration at a temperature range of 120-150C and undergoes sublimation at amospheric pressure at 180-200C, thus providing an anhydrous sublimate.

In this experiment, the crude caffeine is subjected to the sublimation method for purification purposes. The melting point of the sublimate, which serves as the index of purity of the obtained or recovered substance, is then determined through the use of a melting point apparatus. Comparison of the melting points of the impure and the pure caffeine obtained is then done through their melting point ranges. As stated previously, the narrower the melting point range, the purer the substance obtained.

Sublimation is physically defined as the transition of a substance from the solid phase to the gas phase without passing through an intermediate liquid phase. Furthermore, it is an endothermic phase transition that occurs at temperatures and pressures below a substance's triple point in its phase diagram. At normal pressures, most chemical compounds and elements possess three different states at different temperatures. In these cases the transition from the solid to the gaseous state requires an intermediate liquid state. However, the pressure referred to here is the partial pressure of the substance, not the total (e.g. atmospheric) pressure of the entire system. So, all solids which possess an appreciable vapor pressure at a certain temperature usually can sublimate in air (e.g. ice just below 0C). This property of a substance is usefully employed in reverse, as a method of purification. Essentially, the compound is allowed to become a gas and is then solidified on a cool surface. Because the cooling compound does not pass through the liquid phase, the material is not washed from that cool surface. Hence the solid collects on that surface in a form that is free from non-sublimable impurities. Caffeine tetrahydrate (C8H10N4O24H2O) obtained from the previous isolation experiment was used as the sample for the experiment. Theoretically, the substance loses its water of

hydration at a temperature range of 120-150C while it sublimes at amospheric pressure at 180-200C. Thus, it is possible that sublimation could be employed for the purification of the caffeine sample. Carrying out the sublimation of caffeine requires three steps, consisting of the setup, the sublimation, and the retrieval. The first step, which is the setup, involves the assembly of the sublimation set-up, readying it for use and adding the sample to the apparatus. The apparatus used, as shown in the laboratory manual, involves a sand bath, two test tubes, one of which is larger while the other is a bonesil test tube (smaller tube with lip), burner and the rest which are assembled accordingly. The sample of crude caffeine has been spread evenly across the bottom of the larger test tube. By thinning out the sample, a wider surface area is created to expose more of the pure product and facilitate more complete sublimation. The smaller tube (also referred as cold finger) has been positioned about inch from the bottom of the larger tube. When the actual sublimation begins after the setup, a sublimate will begin to form on the surface of the cold finger. Due to the nature of gravity and crystallization, the product will grow downward towards the crude sample. This distance approximation is therefore necessary to ensure that the pure product obtained after the process does not come in contact with the crude sample and ruin the process. The distance may be increased according to the expected amount of product to be collected but the goal is to get the cold finger as close as possible to facilitate sublimation, without endangering the final product. About 1 inch of the larger tube was immersed in the sand bath and was then heated to a temperature of 150C to remove all moisture from the crude caffeine sample. Once the setup has reached the temperature indicated, the sublimation step comes next. Sublimation is also called as vacuum sublimation because it is usually carried out at low pressures. In this process, caffeine is heated in a container under reduced pressure. This method of heating usually makes the solid sublime directly into a gas without first melting into a liquid. Considering the phase diagram of caffeine,

we can see what happens when an attempt is made to heat caffeine at atmospheric pressure. The blue line parallel to the temperature axis at 1 atm of pressure indicates that the caffeine will first melt into a liquid and only then evaporate to a gas. This is unacceptable if sublimation is the process desired, and thus reduced pressures are used in sublimation. At lower pressures, substances will transition directly from a solid to a gas without passing through a liquid phase. As shown by the green line, caffeine when heated under reduced pressure sublimes into a gas. This is the rationale for using a vacuum in sublimations. Also, it will be noted that substances sublime at lower temperatures as pressures are lowered. Therefore, lowering the pressure also reduces the risk that a substance will be destroyed by intense heat during sublimation. Mild heating is the final component necessary for complete sublimation of caffeine, which was done at a temperature of about 180-200C .Heating adds energy to the crude sample and brings its components closer to their desired vapor pressure for sublimation. The amount of heat used is enough to only bring the pure product to its desired vapor pressure. Excess heat would sublimate the entire crude sample and prevent pure caffeine from separation. Shortly after heat has been applied, at about 190C, pure product begins to crystallize on the underside surface of the cold finger. As observed, pure caffeine is a small, white solid, and is easily distinguished by its dangling, needle-like crystal formations whereas the impurities, which are usually of heavier molecular weight and do not evaporate as easily, are left behind on the bottom of the tube as a black-brown colored gum or tar. Due to the delicate nature of crystallization, the set-up is kept completely still to avoid knocking the pure caffeine back into the crude sample. When no additional product crystallizes on the cold finger, sublimation has been completed, and the sample is ready for retrieval. Retrieval involves preparing the set-up for the collection of the pure sample of caffeine, and the actual collection itself. This step in the process is probably the most difficult since, as briefly mentioned above, the delicate nature of crystallization makes the sample very fragile, and must be handled very carefully. Once the cold finger with the sample of pure caffeine has been removed from the larger tube, the caffeine can be collected by simply scraping it off of the cold finger with a spatula into its desired container. Sublimation is the easiest way to effectively separate a solid substance from other solid impurities, as long as those impurities have a vapor pressure (a property related to the boiling point) that is sufficiently different from the desired product. Aside from this, sublimation is advantageous to facilitate since no solvent is required to be used, it removes occluded materials and is often faster than other purification methods for instance, recrystallization. However, certain limitations are encountered also such as the reduced pressure needed and the vapor pressure difference between the pure material and the impurities that must be considered. Sublimation is also best used only on small amounts of sample since product loss in transfer and collection is minimal. After retrieval, the final product obtained weighed about 0.0170 g. A small amount was then taken for melting point determination using the melting point apparatus. The obtained temperature range was 232.9-235.7C which is approximately close enough to the theoretical value which is 236C. The slight deviation from the theoretical value may be accounted for some impurities that may have retained even after the sublimation process or those that may have accidentally occluded when the pure sample was being transferred to the container. Thus, the sublimate is still impure and needs further purification. Also, the percent recovery calculated was about 15.51%, which is relatively small. This may have been higher if unavoidable loss of product during the retrieval process has not occurred. Although, sublimation was still proven as a fast, efficient way of purifying impure solids.