Impact of Proper Solvent in the Purification of Organic Products Brandon Gieler Organic Chemistry Lab 347L TA: Mahin

Behnia University of Nevada, Las Vegas December 5th, 2011 Abstract The results obtained in this report assess the selectivity of a proper solvent for use in the purification process known as recrystallization. A good solvent is necessary along with proper cooling procedures for a successful recrystallization. Without such precautions, results will contain impurities or poor recoveries, which will take away from the purity value of the recovered organic compound.

Introduction One of the most essential techniques organic chemists use is the recrystallization procedure. This technique is mainly used in the purification of organic compounds, yet it has many other commercial uses as well, such as accelerating the process of forming crystals like table salt, etc. By manipulating a solvent to have restricted solubilizing properties, scientists can separate compounds by their ability to dissolve in certain conditions. To do so, one must not only understand the organic compound being purified, but

they must also know how to choose a solvent classified as a good solvent. A good solvent is a solvent that is similar in composition to the material that will be purified, however not too similar, as it will react with the organic compound and remain as a solution. As all good organic chemists know, like dissolves like when it comes to solubility, but there is a way to force the solvent to break down similar compounds. If a solvent is taken that has similar properties to the impure compound, such as polarities, but retains a charge slightly opposite to the solute, then another force acting on the compound can create a reaction. A great force that scientists can easily manipulate is heat. Controlling the heat of the solution, will dictate the dissolving power of the solvent because it adds energy needed for bonds to break. As this solvent is heated, the bonds of the impure organic compound begin to break and bond to the solvent forming a mixture. This mixture is completely liquid and by controlling the heat added once again, the temperature can be lowered, which will return the organic compound to its pure state. Although this procedure seems simple enough, it is quite precise. This technique requires the controlled cooling of the solution, so that the impurities removed will not be once again captured in the reformed crystals. As stated in the crystallization handout prepared by professor Behnia, a successful recrystallization therefore requires slow cooling. This is referring

to the capture of impurities by a rapid cooling. During rapid cooling, impurities in a liquid mix with pure substances and create impure compounds in a process known as precipitation. Precipitation is useful in some laboratory experiments, yet when creating pure compounds, it must be avoided at all costs. So to begin recrystallization properly, a good solvent is used and has the following characteristics: it must have a similar polarity to the compound that will be purified, it must allow for high solubility at high temperatures and low solubility at low temperatures, and it must not react with the organic compound to create a completely new compound. By utilizing these guidelines, the following experiments were performed and the purity of the recrystallized compounds was analyzed.

General Methods and Materials All reactions and experimental set-ups were prepared with sterile glassware from the chemistry lab. Reagents were provided by the instructor and kept in sealed containers. Since reagents were used as is, no preparation of compounds was necessary. Crude acetanilide was previously prepared in a manner that introduced contaminants to the organic compound. Contaminants included, but were not limited to: coffee grinds, saw dust, brown sugar, etc.

General Procedure The Experiment began with obtaining the impure compounds. Crude acetanilide was gathered and weighed on a digital scale. 7.40 mmol was required which is equivalent to about 1.000g, however due to human interaction, approximately 1.003g was obtained. Acetanilide served as the impure compound to be purified using a macro scale approach. 9-fluorenone is an impure compound containing fluorene and was used for micro scale purification and recrystallization. 0.58g of 9-fluorenone was gathered and set aside for the micro scale recrystallization. Recrystallization of acetanilide proceeded first. Acetanilide was transferred to a clean, dry 50 mL Erlenmeyer flask and 18-20 mL of water was added. Water was used as a good solvent in this case. Previously, the instructor tested solvents for solubility and the following were found to be true. Ethanol is a good solvent when breaking down acetanilide, however this reaction happened too quickly and at room temperature. These facts state that ethanol is a powerful solvent, but it is not classified as a good solvent in relation to recrystallization. Water is a bad solvent at room temperature, yet when heat is applied, the acetanilide compound will break down. This addition of heat catalyzed the break down of the impure

acetanilide and as heat is removed, the product can form. In terms of recrystallization, water is a good solvent. With these facts in hand, water was used as a solvent and the Erlenmeyer flask containing the impure compounds in water was heated up. By applying heat the insoluble compound began to break down and transformed into a brownish liquid state with brown particles floating around. The solution was allowed to cool for approximately 60 seconds followed by the addition of 100mg of charcoal (decolorizing carbon). While swirling the flask, 200 mg of celite was added. These two materials removed the color from the mixture as well as the fine impurities. A gravity filtration apparatus was then used to remove the larger particles within the mixture. This apparatus was set up by using a glass funnel, filter paper, 125mL Erlenmeyer flask, and a piece of copper wire. The Erlenmeyer flask in this set up was set below the filtration device on a hot plate and 5 mL of water was added. This water will create a light steam as heat is applied and will keep the mixture from going through premature crystallization inside the filter. The acetanilide mixture was reheated and poured through the filtration system. This new mixture was clear and free from visible impurities. After heating this clarified mixture one more time for about 2 minutes, the cooling process was to begin. The hot mixture was removed from the heat and wrapped in aluminum foil. It was then allowed to

cool at 23C undisturbed. Slow cooling is crucial in this step for a proper recrystallization to occur. After the solution has properly cooled, crystals were present in the solution. Recrystallization had successfully occurred and this crystallized mixture was allowed to rest in an ice bath for approximately 15 minutes. A vacuum filtration apparatus (Technique #8, Pavia) was set up and the crystallized mixture was poured through it. This technique removes most of the moisture from the crystallized compound, however the recovered compound was allowed to air-dry to get rid of the residual moisture. The recovered and dried acetanilide was measured and tested for purity by analyzing it melting point. Recrystallization of acetanilide was completed and purification of fluorene commenced. The purification of fluorene proceeded using the same methods as acetanilide, however micro scale techniques were applied. A good solvent must be found to proceed with recrystallization and the discovery of this solvent was left to the students. A test system of four test tubes was set up in a rack and 50mg of 9-fluorenone was added to each tube. 0.5mL of ethanol, water, and toluene were added to each tube respectively, leaving the fourth tube as a control. Solubility was assessed and the following results were obtained: tubes containing methanol and water had no reaction at 23C and the tube containing toluene had completely dissolved at 23C. This

preliminary test concluded that toluene would not be a good recrystallization solvent. After the addition of the solvent, these tubes were heated in a hot water bath and showed the following results: the tube containing water showed no reaction at 55C, the tube containing toluene remained dissolved at 55C, and the tube containing methanol began to break down as temperature increased until it fully dissolved at 55C. Using these results, methanol was deemed as a good solvent for this experiment. 0.58g of 9fluorenone was added to a Craig tube along with 0.5mL of methanol and was heated in a hot water bath. Methanol was added during this heating process as necessary to prevent complete evaporation of the solution. After the materials were dissolved, the solution was removed from the heat and allowed to cool at 23C undisturbed. The solution crystallized slightly and when the solution was sufficiently cooled, the tube was placed in an ice bath for five minutes to ensure maximum recovery of purified products. A Teflon plug was added to the Craig tube and placed in a centrifuge for two minutes. After centrifugation, the recovered mass of pure fluorene was obtained and air-dried on a watch glass. This mass was measured and tested for purity by analyzing its melting point.

General Product Analysis

Purity of recovered organic compounds was assessed by melting point test. When testing for melting point, it is possible to analyze the purity of a substance by comparing its complete break down into liquid state versus the first droplet of liquid forming. If the difference in these two states is a narrow range (~0.5-2C) then it is most likely a pure solid compound. If the range is wider (3-10C) then there are most likely impurities present in the compound. The results of these melting points are also compared to known melting points, which can confirm pure results. According to the theoretical melting points of the pure compounds and the variable melting points obtained from the recovered compounds, the recovered materials were not 100% pure, however they were of high purity. The ranges of the melting points obtained were relatively narrow, yet they did not match exactly to the theoretical melting points. This confirms a good recrystallization occurred, but the experiment was not perfect. The following data is a collection of the results obtained from the purification of acetanilide and fluorene.

Table 1 Purification by Crystallization Recovered Recovered Entry Reagent (Crude) (Pure) Mass Yield 1 2 Acetanilide Fluorene 1.003g 0.058g 0.542g 0.380g 54.0% 65.6%

B.P. 109-111C 109-110.2C

Table 2 Solubility of Fluorene Solubility Methanol Entry Conditions (B.P. 65C) 1 2 At 23C Heat Applied Insoluble Soluble Discussion

H2O (B.P. 100C) Insoluble Insoluble

Toluene (B.P. 111C) Soluble Soluble

The results shown demonstrate the proper use of a good solvent and the importance of first determining which solvent will be best for recrystallization. If a poor solvent were used then recrystallization would not be possible. If the solvent were too strong, the organic compound would remain in a dissolved state and if the solvent were too weak, it would not be possible to separate the impurities from the compound. The chart below (figure 1) shows a rough comparative analysis of the solvents used in the recrystallization of fluorene and its effectiveness as a recrystallization solvent. Along with a good solvent proper cooling is absolutely necessary, which means the solution must be cooled slowly. By cooling the solution slowly, it can be ensured that impurities are not caught in the reformed crystals. Although this technique is not perfect, it is a staple to organic chemistry and provides results with high purity level.

Figure 1. Rough comparative analysis of solvents used in purification of fluorene References Experiment #3 part C: Mayo, D.W., Pike, R.M., Trumper, P.K. Microscale Organic Laboratory, 3rd Ed. John Wiley & Sons, Inc.: New York Procedure #6: Behnia, M. CHE347L Organic Chemistry Laboratory, Fall 2011