Experiment 1: Purification of Benzoic Acid by Recrystallization Ariane Pauline Mendoza, JC Hope Carino I.

Abstract

SEJ, Group 1, Ms. Dame Loveliness Apaga 16 February 2013

Recrystallization is used to purify impure solids with an appropriate solvent. The process is summarized into seven steps: (1) choosing the solvent; (2) dissolving the solute using a hot solvent; (3) adding and an activated charcoal; (4) filtering the suspended solids; (5) crystallizing the crystals; (6) collecting the pure solid by filtration; (7) collecting and drying the crystals. The solvent that shall be used must have separate solubilities for both the pure and the impure compounds. Upon heating the solid is disrupted, and then allowing the crystals to regrow upon cooling. A decolorizing agent might be added to remove the colored impurities. Hot filtration is applied when the impurities are insoluble in the solvent. After recrystallization the benzoic acid is collected, dried, and weighed. II. Keywords: solubility, solute, solvent, crystallization, percent recovery, hot filtration

III. Introduction Recrystallization is one of the most valuable techniques used in the laboratory. It aims to purify a solid compound by allowing the compound to be dissolved in the solvent prior to crystallization. It includes other techniques such as filtration and obtaining the percent recovery. In a solution, the component that has the greatest amount is the solvent while the one that has smaller amount is the solute (Katz, 2007). The solubility of solute in a solvent is the maximum amount of the solute that can be dissolved in the solvent at a certain temperature, given that excess solute is present (Brown, 2009). There are factors affecting solubility: (1) solute-solvent interaction; (2) pressure effect; (3) temperature effect. The IFA determines whether dissolution may occur. A polar solvent dissolves another polar solute while a nonpolar solute dissolves in a nonpolar solvent. After dissolution the crystals are allowed to regrow, this time rearranging themselves to form a crystal. The impurities will be left behind in the solution. Techniques like adding a decolorizing agent and hot filtration may be used if necessary, for there are colored impurities and types of impurities (those more soluble in a given solvent than the main component and those less soluble), respectively. IV. Experimental Weigh 0.5 g of impure benzoic acid in a makeshift autoclavable vial: beaker. Then add a small boiling chip and about 100 mL of distilled water (dH2O). Swirl the beaker constantly until the solid dissolves completely. Add more solvent if necessary. Cool the solution by adding few more

drops of dH2O, then add a pinch of activated charcoal. Do not add the latter while the solution is hot. Heat again the solution for few minutes until a change in color is observed and the volume goes down to about 1 mL. Pour the hot mixture quickly into a filter syringe collecting the filtrate into a vial [A].

[A] Figure 1.0 Hot Filtration

Cool the solution at room temperature, and then in an ice bath. Collect the crystals in a preweighed filter paper set on an improvised support [B], then collect the remaining crystals by rinsing the vial with cold water.

[B] Figure 2.0 Filtration of Pure Benzoic Acid

Open the filter paper, fold it with the crystals inside it, and squeeze out the water by inserting it between the folded tissue paper and pressing on it. Let the filter paper and the crystals dry completely and then weigh. V. Results % Recovery of Benzoic Acid: Weight of impure Benzoic Acid .5 g Page 1 of 5

Chemistry 31.1, Purification of Benzoic Acid by Recrystallization

Weight of the filter paper 1.03 g Weight of the filter paper and the crystals 1.10 g Weight of Pure Benzoic Acid .07 g % Recovery = (W pure/W impure)(100%) = (.07g/.5g)(100%) = 14 % VI. Discussion 1. Selecting the best solvent Benzoic acid is a white crystalline substance present in benzoin and other plant resins, and is used as a food preservative (Oxford Dictionary). Its chemical formula is C6H5COOH=C7H6O2. This compound is only slightly soluble in water (0.29-0.34 g/100 mL). In the experiment water is used as the solvent. It has different solubilities for the compound (slightly soluble) and the impurities (insoluble).
Table 1.0 Solvent & Solvent

Heating the solution disrupts the crystal. In this manner the molecules of the pure compound, together with of the impure compound, freely move in the water. This step is prerequisite to crystallization. Heating allows them to break and then regroup upon cooling. This time, the impurities are being outcast by the pure crystal. The solubility of a solid is dependent on temperature (Katz, 2007). The solubility of benzoic acid in water increases as the temperature increases. Adding too much solvent to dissolve the solute will prevent later recrystallization, causing the loss of the product. 3. Decoloration

Figure 3.0 Dissolved Benzoic Acid

Solubility is the amount of solute dissolved in a solvent at a given temperature. There are factors affecting solubility: (1) Polar solvents dissolve polar solutes. Water can dissolve solutes with C=O forming H-bonds (i.e., benzoic acid). Water is both polar and able to form hydrogen bonds. Polar molecules, especially those that can form H-bonds, tend to be soluble in water (Brown, 2009). Substances with similar IFA tend to be soluble in one another. Like dissolves like. (2) The partial pressure effect, which apply mostly to gases. This time, the solubility of solid is not affected by pressure (Brown, 2009). (3) The solubility of most solid solutes in water increases as the solution temperature increases (Brown, 2009). A solubility curve helps in determining the solubility of most solid compounds. The outcome depends largely on the solvent used (i.e., the solid compound must be only slightly soluble in water at room temperature, while being freely soluble in the solvent at higher temperatures). 2. Dissolution of the impure solid

If the solution is contaminated with colored impurities (pink color), it may be treated with a decolorizing agent activated charcoal. Colored impurities are sometimes difficult to remove from solid mixtures even after recrystallization. The activated charcoal has higher surface area to adsorb the impurities. These impurities tend to be insoluble in water prior to the hot filtration. Add only a sufficient amount of activated charcoal. Too much of it may adsorb the impurities, as well as the desired compound. 4. Hot Filtration There are impurities that are insoluble in solvent. In this case, the hot solution must be filtered when it is hot. It is important to perform this immediately after removing the beaker from the burner such that the high temperature is maintained and the benzoic acid remains dissolved in the solvent and doesn't rapidly crystallize. It is important to rapidly pour the solution to the syringe where cotton is plugged. 5. Crystallization In a hot solution the molecules of both the pure and impure compounds move freely. When the Page 2 of 5

Chemistry 31.1, Purification of Benzoic Acid by Recrystallization

solution is cooled the solvent would not be able to hold all the molecules so the molecules will tend to rest on their crystal form. The solute particles must arrange themselves properly to form crystals. With the appropriateness of geometry, the crystal will only facilitate the solute. The cooling must be slow. This prevents the impurities from permanently surfacing the molecules of the solute. The impurities may surround the lattice, but leave after an appropriate geometry comes into place.
Table 2.0 Recrystallization vs. Precipitation

In the experiment, the % recovery is 14 %, which is far less than expected. The following are the possible discrepancies: Differences in the amount of impurities (-) Amount of solvent added (-) Slow [hot] filtration (-) Not fully-dried filter paper (+) The (-) sign indicates decrease in the amount recovered while the (+) sign signifies increase. VII. Guide Questions and Answers (1) List the properties that an ideal solvent should have to perform the purification of organic compound by recrystallization technique. - Does not react with the solid to be purified; - Dissolves the entire compound at its BP; - Dissolves very little/none of the compound when the solvent is at room temperature; - Has different solubility for the compound and the impurities; - Has a BP below the MP of the compound so that the compound dissolves and not melts in the hot solvent; - Has a relatively low boiling point; - Is very volatile, can be easily removed from the crystals. (2) In purifying by crystallization from a solvent, is it advisable to cool the solution slowly or rapidly? Explain. - Slowly. It results to better crystals (i.e., the size of the crystals are neither too small, nor too big). Larger surface areas of the crystals may facilitate adsorption of impurities from the solution. (3) What advantages does water have as a recrystallization solvent? - A polar solvent like water has partial charges that can interact with the partial charges on a polar compound. - At 10 C, 2.1 g of benzoic acid dissolves in 1000 ml of water. But at 95 C, 68 g of benzoic acid is soluble in 1000 ml of water. In short, at different temperatures benzoic acid has huge solubility difference in water. (4) Two students crystallized 10g samples of benzoic acid from water, the first dissolving benzoic acid at 80C and filtering at 10C, the second dissolving at 95C and filtering at 18C . Calculate the quantity of water each student was required to use and the maximum recovery of benzoic acid possible in each case. Student 1

If a hot saturated solution is cooled too quickly, the compound may precipitate instead of crystallizing. A precipitated solute may contain many impurities trapped in the crystal structure. The vial must be rinsed with cold water to collect the remaining crystals. Also, one may add a seed crystal of the solute to start the crystallization of the excess solute. After crystallization, a saturated solution remains (Katz, 2007). If either of the two steps doesnt work, break the vial. 6. Collecting the pure crystals through filtration The pure crystals stay intact in the solution upon crystallization. In order to retrieve these crystals filtration must be executed. In other laboratories the filter paper is fluted in order to more efficiently salvage the exact amount of crystals. 7. Drying and weighing the crystals The weight of the impure benzoic acid is .5 g. The filter paper that was used in filtering the pure crystals is 1.03 g. During the filtration, the pure crystals were left on the filter paper. It has been allowed to dry so that when the paper is weighed, the additional weight will only come from the crystals. The weight read: 1.10 g, which means that the amount of crystals recovered is .07 g. The formula given by the percent recovery says: (W pure/W impure)(100%). The percent recovery determines how much crystals have been recovered from the original impure solid. It is better to obtain a sufficient (neither very low nor very high) percent yield.

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@ 80 C 10 g = 2.75 g X1 ml 100 ml X1 = 363.6364 ml @ 10 C Y1g = 0.21g 363.63 ml 100ml Y1 = 0.7636 g 10 g 0.7636 g = 9.24 g Student 2 @ 95 C 10 g = 6.80 g X2 ml 100 ml X2 = 147.0588 ml @ 18 C Y2g = 0.27g 147.06 ml 100ml Y2 = 0.3971 g 10 g 0.3971 g = 9.60 g (5) A Solid (X) is soluble in water to the extent of 1 g/100 g of water at room temperature and 10 g per 100 g of water at the boiling point. a. How would you purify X from a mixture of 10 g of X with 0.1 g impurity Y, which is completely insoluble in water and 1 g impurity Z having the same solubility characteristics in water as X? - Dissolve the mixture in 100 g water and heat until boiling. Cool the mixture to room temperature then filter to separate Y. - Add water to the filtrate up to 100ml. Heat the mixture again until boiling until all crystals dissolve. Slowly cool the mixture to room temperature. Filter the mixture. - The residue left on the filter paper is the purified X crystals. - The formation of impurity Z is insignificant since it is minimal in quantity (1g) and has a different lattice structure from the solid X structure thus excluding Z in crystal formation. b. How much pure X could be obtained after one recrystallization from water? 10g 1g x 100% = 90% 10 g - Since the solubilities of different solutes are independent of each other, at room temperature, it would be assumed that 1 g of solutes X and Z would dissolve. So, 9 g of pure X solute will crystallize.

c. How much pure X could be obtained after one recrystallization from a mixture of 10g of X with 9 g of Z? - All X and Z must be dissolved. The solubility of X and Z are independent of each other and to dissolve all crystals, solid X is used as basis for it is present in a larger amount. 10g = 1g X = 1000 g water X g 100g - To ensure that Z doesnt crystallize back, the final amount of water must ensure that solute Z crystals remain dissolved in water under room temperature. Heat the solution. 9g = 1g Y= 900 g water Y g 100g - The solution is slowly cooled until crystals are formed. Z g = 1g Z = 9 g solid 900g 100g - In 900 g water, 9 g of solutes X and Z are dissolved which means only 1 g of pure solid X can crystallize from the solution. d. Based on the results obtained, what is suggested about the use of crystallization as a purification technique? - The technique is diffidult for it relies on the differences in solubility. VIII. Conclusions & Recommendations Recrystallization is used for purifying solid compounds, which includes different laboratory techniques. The solid is heated to disrupt its crystal and then cooling regrows the crystals. Then, the pure crystals are filtered on a pre-weighed filter paper, which is then weighed after drying. The weight determines the percent recovery. Choosing the appropriate solvent to dissolve the impure solid is essential, as well as the solubility of the solid in the solvent. Recommendations include: using another type of impure solid to be purified, another type of impurity, as well as another type of solvent that shall be used for purification. IX. References Brown, T. L. et. al. (2009) Chemistry: The Central th Science, 12 Edition. The Solution Process. United States of America (pp. 514-526). Katz, D. 2007. The Solubility of a Salt in Water at Various Temperatures. Legaspi, C. et. al. (2009) Experiment # 1:

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Purification of Benzoic Acid by Recrystallization [PPT]. Retrieved from https://www.google.com/search?sclient=psy &hl=fil&biw=1279&bih=600&source=hp&q= group+1recrystallization+ppt&btnG=Hanapin Organic Chemistry at CU Boulder. (2013). Crystallization. Retrieved from OrgChem Colorado Online http://orgchem.colorado.edu/Technique/Pro cedures/Crystallization/Crystallization.html Recrystallization Introduction. (n.d.). CHM220 Recrystallization and Melting Point. Retrieved from CHM 220 website http://classes.kvcc.edu/chm220/Recrystalliz ation/prelab/introduction.htm Recrystallization Technique. (n.d.). Proper Purification of Crystalline Solids. Retrieved from Rhodium website http://www.erowid.org/archive/rhodium/che mistry/equipment/recrystallization.html Roberts, R. et. al. (1979) Modern Experimental rd Organic Chemistry, 3 Edition. Recrystallization. Philadelphia (pp. 49-59) I hereby certify that I have given substantial contribution to this report. _______________________ Ariane Pauline Mendoza _______________________ JC Hope Carino

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