EXP 3.4 Properties of Solvents and Recrystallization of Organic Solids EXP 3.

7 Solvent and Polarity Effects in Thin Layer Chromatography Chelsea Schwartz CHEM 213 Dr. Lewis 6/4/13

EXPERIMENT 3.4 PROPERTIES OF SOLVENTS AND RECRYSTALLIZATION OF ORGANIC SOLIDS ABSTRACT: In this experiment, the solubility of organic solids in various solvents was determined and the data showed that trans-stilbene is nonpolar, 9-fluorenone is moderately polar, and benzoic acid is polar. This was seen based on the concept of like dissolves like meaning that polar solutes tend to dissolve in polar solvents and nonpolar solutes tend to dissolve in nonpolar solvents. Also, a suitable solvent or solvent pair was selected to recrystallize an unknown, specifically a mixture of toluene and hexane as the solvent worked best to form pure benzoic acid crystals from an impure compound of benzoic acid and 9-fluorenone. The melting point of the remaining benzoic acid was determined and was 122.07- 123.97 C. INTRODUCTION: The main purpose of this experiment was to determine the solubility of an organic solid, specifically transstilbene, 9-fluorenone, and benzoic acid, in various solvents such as hexane, toluene, acetone, ethanol, and water. This was done by seeing if each solute would turn out to be insoluble, partially soluble, or soluble in each of the five solvents in a hot and cold environment. The solubility of a solid, liquid, or gas (the solute) is when it forms a solution by dissolving in a solid, liquid or gas (solvent). This depends on many different chemical and physical properties of both the solute and solvent, in this experiment mainly polarity. Polarity in a molecule is the separation of an electric charge causing a dipole moment and depends on the electronegativity of the atoms. When there is a dipole moment the molecule is said to be polar and when there is an equal sharing of electrons or no dipole moment the molecule is said to be nonpolar. Furthermore, recrystallizing an unknown from a suitable solvent was another component of this experiment. Recrystallization is a widely used technique to purify chemicals. This is done by dissolving the compound and the impurity in a solvent then heating and cooling the solution to allow the formation of crystals of the pure compound and discarding the impurity. To be able to see how pure a compound is the melting point can be determined and compared with the known melting point of the pure compound. If there is broad melting point range this shows that the compound has impurities left compared to a smaller range. The melting point is the temperature when the solid state of a compound changes to its liquid state. Below is some basic background information on the solutes and solvents used in this experiment (Schoffstall) SOLUTES:

TRANS-STILBENE FW: 180.25 g/mol MP: 124 C BP: 305-307 C Density: 0.97g/mL

BENZOIC ACID FW: 122.12 g/mol MP 122 C BP 249 C Density: 1.27 g/mL

9-FLUORENONE FW: 180.2 g/mol MP: 84 C BP: 342 C Density 1.13 g/mL
SOLVENTS

HEXANE FW: 86.18 g/mol MP -95 C BP 69 C Density 0.659g/mL

TOLUENE FW: 92.14 g/mol MP: -93 C BP 110-11 C Density: 0.865 g/mL

ETHANOL FW: 46.07 g/mol MP: -114 C BP 78 C Density: 0.789 g/mL

ACETONE FW: 58.08 g/mol MP: -94 C BP 56 C Density 0.791 g/mL

WATER FW: 18.02 g/mol MP: 0 C BP 100 C Density: 1 g/mL

(Wikipedia) EXPERIMENTAL: PART A: SELECTING AN APPROPRIATE SOLVENT MATERIALS 15 dry clean test tubes Test tube rack Pipets 10-20 mg of trans- stilbene, 9-fluornone, and benzoic acid (solutes) Hexane, toluene, acetone, ethanol, water (solvents) Spatula Ring stand

Hot plate Beaker Magnetic stirrer

PROCEDURE: All of the 15 test tubes were labeled with the solute and solvent that was going to be added. Ten to 20 mg of each solute (trans-stilbene, 9-fluornone, and benzoic acid) was measured and added to 5 of the test tubes. Ten drops of each solvent (hexane, toluene, acetone, ethanol, and water) were added to each test tube containing the three different solutes. Each of the test tubes were mixed to see if the solute would dissolve in the solvent and was marked I for insoluble, p for partially soluble, and s for soluble. The solutions that were insoluble or partially soluble were tested in a hot environment by being placed in a beaker on a hot plate containing a magnetic stirrer inside. Each solution was again classified as insoluble, soluble, or partially soluble in the hot environment. PART B: MICROSCALE RECRYSTALLIZATION OF AN ORGANIC SOLID MATERIALS Trans-s tilbene, 9-fluronone, benzoic acid (solute) Pipet Medium Test tubes Hot plate Magnetic stirrer Ice bath Balance and weigh boats Beaker Ring stand / clamps Capillary tube PROCEDURE Two hundred milligrams of a solute, for example benzoic acid, was weighed and added to a medium test tube. A solvent, in this case hexane, was added to another medium test tube. Both test tubes were placed in a hot water bath in a beaker held up by two ring stands. When both began to reflux, a pipet was used to transfer the hot solvent to the solid. Once the solid dissolved in the solvent after the solvent was continuously added and swirled, the test tube was removed from the hot water bath and cooled to room temperature. To complete the recrystallization process, the test tube was placed in an ice bath. To finish, the crystals were washed with ice cold solvent. The above procedure was repeated except instead of using a pure compound, a compound with an impurity was used. A mix of hexane and toluene was used as the solvent to remove 9-fluronone (started with 0.0250g) from benzoic acid to form pure benzoic acid (started with 0.150g) crystals. When the crystals were obtained, the melting point was determined by taking the crystals in a capillary tube and placing them in a melting point determining apparatus. Once the crystals began to melt, the temperature was recorded (Schoffstall).

FIGURE 1: The general set up to complete the recrystallization process. Instead of using flaks test RESULTS: tubes were used held by a ring stand. Table 1
Hexane Hot S S S Cold I P I Toluene Hot S S S Cold S S S Acetone Hot S S S Cold S S S Ethanol Hot P S S Cold I P S Water Hot I I S Cold I I P

Trans-stilbene 9- Fluorenone Benzoic acid

Table one show the solubilitys of the three organic solutes in five different solvents. The s stands for soluble; the I stands for insoluble and the p stands for partially soluble.
The data above displays the concept of like dissolves like. In other words, the general trend is that polar solutes tend to dissolved in polar solvents and nonpolar solutes tend to dissolve in nonpolar solvents. MELTING POINT AFTER RECRYSTALLIZATION OF AN IMPURE COMPOUND The observed melting point of the benzoic acid crystals from the experiment: 122.07C- 123. 97 The expected melting point is 122 C The temperature started at 105 C and ended at 135 C with a rate of 5 C/ minute. DISCUSSION: Based on the data from part A, polar solutes tend to dissolve in polar solvents and nonpolar solutes tend to dissolve in nonpolar solvents. Trans-stilbene was determined to be nonpolar because of its structure. It has very little to none of a dipole moment because carbon and hydrogen have basically the same electronegativity values. Also, trans-stilbene tended to dissolve in nonpolar solvents such as hexane, moderately polar solvents such as toluene and acetone, but not more polar solvents such as ethanol and water. 9- fluorenone was determined to be moderately polar also because of its structure due to the fact it has an electronegative oxygen and also because it tended to be soluble in moderately polar solvents. Lastly, benzoic acid was determined to be polar because of its structure containing a hydroxyl group and also being soluble in very polar solvents such as ethanol and water. Overall, trans-stilbene was the most nonpolar, 9-fluorenone was moderately polar and benzoic acid was polar. The polarity of the solvents going from nonpolar to most polar was hexane, toluene, acetone, ethanol, and water.

When finding a good solvent for recrystallization it is important to use a solvent that the solute will dissolve in at the boiling point but only be partially soluble or insoluble at room temperature. For a nonpolar solute such as trans-stilbene, a moderately polar solvent such as toluene or acetone would work best. 9-fluorenone is a moderately polar solute therefore a slightly more polar solvent would work best, such as acetone. Benzoic acid is polar therefore water would work for recrystallization or a nonpolar solvent such as hexane would work as well. When performing recrystallization using pure benzoic acid, hexane worked well because the benzoic acid was soluble in hexane when it was heated but insoluble when cold. When performing recrystallization on the impure compound of benzoic acid containing 9-flurenone, a mix of hexane and toluene worked best because 9-fluorenone was soluble in both hexane and toluene in both hot and cold environments but benzoic acid was insoluble in hexane at a cold temperature, which allowed for pure benzoic acid crystals to form and 9-fluorenone to be discarded. This was proven to work well because the melting point of the benzoic acid was determined to be in the range of 122.07 C 123.97 C, which is extremely close to the known melting point value of 122 C. CONCLUSION: In conclusion, this experiment was very successful. The solubility of each solute followed the general trend of like dissolves like. Also, the recrystallization of benzoic acid was very successful because it came out pure and had basically the same melting point as the expected melting point of benzoic acid.

EXPERIMENT 3.7: SOLVENT AND POLARITY EFFECT IN THIN LAYER CHROMATOGRAPHY ABSTRACT Thin layer chromatography was used to separate trans-stilbene, 9-fluorenone, and benzoic acid in four different solvents. All three compounds had the lowest eluting power in hexane and the highest eluting power in acetone. All three compounds had an intermediate eluting power with ethanol and ethyl acetate. When transstilbene, 9-fluroenone, and benzoic acid were mixed together, a solvent of 60% hexane and 40% acetone worked best for the separation of each of the three compounds. INTRODUCTION: The purpose of this experiment was to analyze the factors that determine the rate of elution of organic compounds, the relationship of polarities and there Rf values and solvents, and be able to separate a mixture by selecting an appropriate solvent. Thin layer chromatography is a widely used technique to separate the components of a mixture. It is important because it helps with analyzing the compounds of a mixture and determining its purity. The specific thin layer chromatography method that was used in this experiment was adsorption chromatography. The stationary phase, which is the adsorbent, was a silica gel plate and the eluent is the solvent. The underlying factor of this experiment was polarity because the silica gel plate was polar, therefore strongly binding more polar compounds than nonpolar. The polarity of silica gel plate, the solvent, and the solute all play an important role on how far the solute will travel. The four solvents, also known as the mobile phase in chromatography, were hexane, ethyl acetate, acetone, and ethanol. The three solutes were trans-stilbene, 9fluorenone, and benzoic acid. In general, to perform thin layer chromatography, the compound is made into a solution and spotted close to the bottom of the TLC plate. It is then placed in a chamber with a solvent and the distance traveled by the compound is analyzed. This depends on the relative affinity of the compound for the silica gel plate compared to the solvent. To be able to understand the end result the rate of elution, known as the Rf value, is determined. This is the solute distance divided by the solvent distance. The structures of all the solvents and solutes and some properties are listed on page one and two with the exception of ethyl acetate, which is shown below (Schoffstall).

ETHYL ACETATE FW: 88.11g/mol MP -83.6 C BP 77.1 C Density 0.897 g/mL

(Wikipedia) EXPERIMENTAL: PART A: DETERMINING THE EFFECT OF POLARITY ON ELUTION MATERIALS: 4 -400 mL beaker Capillary tube Filter paper Hexane, ethyl acetate, acetone, ethanol (solvents) Aluminum foil Silica gel TLC plate Trans-stilbene, 9-fluorenone, benzoic acid (solutes) Methylene chloride UV light Vials

PROCEDURE: Four 400mL beakers were lined with filter paper and approximately 10mL of each solvent was placed in each of the four beakers. Aluminum foil was placed on the top of the beaker. Four silica gel plates were cut 5cm X 10cm and a line was drawn with pencil approximately 1cm from the bottom of the plate. Between 1-2mg of each solute was dissolved in 10 drops of methylene chloride in separate vials. A capillary tube was used to spot each of the three solutions on each of the four silica gel plates on the line that was drawn. Each plate was viewed under a UV light to make sure there was a high enough concentration of the compound on the plate. Each TLC plate was placed in the beakers containing the solvent so the solvent would be just below the spots. After the solvent rose approximately 0.5 cm from the top of the plate due to capillary action, the TLC plates were removed, dried, and analyzed under the UV light. The distance of the solute and solvent were measured and the Rf values were calculated. PART B: SEPARATION AND IDENTIFICATION OF COMPONENTS OF A MIXTURE OF TRANS-STILBENE, 9-FLUORENONE, AND BENZOIC ACID PROCEDURE: A mixture of all trans-stilbene, hexane, and benzoic acid was created. Two silica gel plates were cut 5cm X10cm and a line was drawn in pencil 1cm from the bottom. The mixture of the three compounds was dissolved into THF. Two beakers were lined with filter paper and in one beaker 6mL of hexane was added with 4mL of acetone while the other beaker contained 4mL of hexane and 6mL of acetone. The TLC plates were spotted with the solution and placed into the beakers with aluminum foil covering the top. Once the solvent reached approximately 0.5cm from the top of the plate, the plate was removed, dried, and analyzed under a UV light. The Rf values were calculated for both (Schoffstall). RESULTS:

Calculating Rf values Rf = distance traveled by solute/ distance traveled by solvent Example: (trans-stilbene and hexane) = 1.7cm/ 5.8cm= Rf= 0.293

Table 1
Solvents Hexane Ethyl acetate Acetone Ethanol Trans-stilbene 0.293 0.790 0.885 0.684 9-fluorenone 0.368 0.747 0.885 0.795 Benzoic acid 0 0.722 0.885 0.819

Rf values for trans-stilbene, 9-fluorenone, and Benzoic acid in various Table 2

Rank 1 2 3 4 Trans-stilbene Acetone Ethyl acetate Ethanol Hexane 9-flurenone Acetone Ethanol Ethyl acetate hexane Benzoic acid Acetone Ethanol Ethyl acetate Hexane

The rank of solvents in terms of their eluting ability of each solute with 1 being the highest eluting power and 4 being the lowest eluting power. The higher the Rf value is the higher the eluting power. Table 3
Solvent Hexane Acetone Ethyl Acetate Ethanol Compound with the lowest Rf value Benzoic acid All equal Benzoic acid Trans-stilbene Compound with the intermediate Rf value Trans-stilbene All equal 9-fluorenone 9-fluorenone Compound with the highest Rf value 9-fluorenone All equal Trans-stilbene Benzoic acid

The rank of each compound for each solvent used in terms of increasing Rf values.

Figure 1: The chromatograms of each of the three compounds with each of the four solvents going in the order (left to right) Hexane, ethyl acetate, acetone, and ethanol. DISCUSSION:

DISCUSSION: Based on the data from this experiment trans-stilbene can be classified as nonpolar, 9-fluorenone as moderately polar, and benzoic acid as polar. As polarity increases the dielectric constants increase as well. Hexane is the least polar with the lowest dielectric constant, 1.88, then ethyl acetate, 6.02, followed by acetone with a dielectric constant of 20.7, and finally the most polar solvent, ethanol, 24.3. Hexane can be classified as nonpolar, ethyl acetate as moderately polar and then acetone and ethanol as polar. Polarity affects the eluting abilities of the solvents, which can be seen from table 2. A greater Rf value corresponds with a higher eluting ability. Based on the data, the general trend was that nonpolar solvents, such as hexane, had a lower eluting ability, compared to more polar solvents, such as acetone and ethanol, which had a higher eluting ability and greater Rf values. The reasoning behind this could be that the silica gel is polar, therefore a more polar solvent would be needed to cause the solute to travel down the plate instead of binding to the silica gel plate. The way polarity affects eluting ability can also be seen in table three. A more polar compound such as benzoic acid had a lower eluting ability with a nonpolar solvent, such as hexane, because the benzoic acid would bind to the polar silica gel plate instead of traveling with the nonpolar solvent. On the other hand, benzoic acid had the highest eluting ability with ethanol, which was the most polar solvent, compared to the other three solvents. It was interesting to see that all three compounds had the same eluting ability with acetone. The reasoning behind this could be that acetone was polar enough to cause all three compounds to travel down the plate and not bind to the silica gel but was not polar enough to cause a distinguishable separation between the three solutes. When using a silica gel plate, nonpolar compounds travel faster because polar compounds tend to adhere to the silica gel plate because it is polar. This is again demonstrating the concept of like dissolves like. Furthermore, polar solvents have a greater eluting ability because polar solvents will be able to carry both nonpolar and polar compound. Although, if a compound is moving too quickly switching to a less polar solvent would be beneficial and if a compound is moving too slowly then using a more polar compound would be beneficial. In part B of the experiment, trans-stilbene, 9-fluorenone, and benzoic acid were mixed together and the data showed that the 60:40 ratio of hexane to acetone was better than the 40:60 ratio of hexane to acetone when separating the compounds. The 60:40 ratio of hexane to acetone had a more clear and distinguished separation with better Rf values. The 40:60 ratio of hexane to acetone did not separate the components very well, but this could have been due to a source of error, such as adding too much of an initial spot on the TLC plate of the original solution. This combination of solvents was chosen because hexane was the least polar and caused no movement of benzoic acid, but acetone caused an equal eluting ability of all three compounds, so by combining the two the end result would end up being moderately polar. If water was added to the solvent, the chromatogram would have been harder to distinguish because water is more polar than both hexane and acetone, therefore would have possibly caused too much traveling of the compounds to be distinguished. CONCLUSION: In conclusion, thin layer chromatography is an extremely beneficial technique for separating mixtures for analysis and determining how pure they are. Polarity is one of the main factors that plays a role in chromatography and is fundamentally based on the concept of like dissolves like . WORKS CITED.

Wikipedia: The Free Encyclopedia. Wikimedia Foundation. Web. 5 June. 2013. http://en.wikipedia.org/wiki/
Schoffstall, Allen M., Barbara A. Gaddis, and Melvin L. Druelinger. Microscale and Miniscale Organic Chemistry Laboratory Experiments. 2nd ed. N.p.: McGraw-Hill Companies, 2004. Print.