ACID BASE EXTRACTION The purpose of this lab is to demonstrate the influence of pH on the water solubility of certain organic compounds. These properties will be illustrated by the separation of a mixture containing a carboxylic acid, an amine, and a neutral organic compound. This “macroscale” experiment will use a separatory funnel for extractions. Most organic carboxylic acids (with more than 5 carbons) are not very soluble in neutral water. ‘Treatment of a carboxylic acid with dilute aqueous NaOH produces the corresponding sodium carboxylate salt. Due to its ionic character, the sodium carboxylate salt is soluble in water but not very soluble in organic solvents. If the basic solution is then made acidic by addition of HCI, the sodium carboxylate salt will be converted to the original carboxylic acid, which is not water soluble. NaOH HCI RCO,H > RCO" Nat > RCO,H + NaCl not water water soluble not water soluble soluble Likewise, most organic amines are not soluble in neutral water. Treatment of organic amines with aqueous HCI produces the corresponding ammonium salt, The ammonium salt is soluble in water but not very soluble in organic solvents. If the acidic solution is then made basic by the addition of aqueous NaOH, the ammonium salt will be converted back to the original amine, which is not water soluble. HCI NaOH RNH, > RNH;* Cr > RNH, + NaCl not water water soluble not water soluble soluble By taking advantage of these solubility properties, it is possible to separate a mixture containing acidic, neutral, and basic components using acid and base extractions. Before beginning, make sure that you are familiar with the proper techniques for using a separatory funnel (Technique 12.7). You should also make a flow chart that outlines the separation that you are performing (see for example p. 687). 10‘The exact identity of your separation mixture will not be known and will be determined by melting point after separation. The mixtures (bottles #1-6) will contain one acid, one amine and one neutral. The possible acid components of your mixture are benzoic acid and toluic acid. The possible amines are ethyl 4-aminobenzoate and dimethyl aminobenzaldehyde. The possible neutral compounds are p-dibromobenzene and benzophenone. ye Oyo. wn) cove, a) cer theme ® ate — ‘cH, tice Haneefacapenaiiys Extraction procedure: Dissolve 1 gram of a mixture of an acid, base and neutral (from bottles #1-6) in 15 mL of diethyl ether. (Note: keep ether solutions in the hood when ever possible--this will help keep ether fumes from building up in the lab). Transfer the ether solution to a separatory funnel and add 5 mL of | M HCI (Be sure to use IM and not 6 M HCI which will be used in a later step!). Gently shake the separatory funnel for several minutes, venting it frequently to avoid the build up of pressure. Place the separatory funnel in a ring stand and allow the ether and aqueous layers to separate. Uncap the funnel and drain the ower aqueous layer into a flask. Repeat the extraction with another 5 mL of 1 M HCI. Save the ether layer in the separatory funnel for later use. Combine (in a beaker) and cool the acidic aqueous extracts in an ice-water bath. Add 6 M NaOH (~ 2 mL) until the aqueous layer is basic (use pH paper to confirm). Collect the precipitate on a Buchner funnel by vacuum filtration (see Figure 8.5, pg 622). Wash the filtrate with cold water (~ 2 mL) and allow it to air dry until the next period. Extract the saved ether solution twice with 5 mL of 1 M NaOH. Again, save the ether layer in the separatory funnel. Combine and coo! the basic aqueous extracts in an ice-water bath. Add 6M HCI (~ 2 mL) until the aqueous layer is acidic. Collect the precipitate on a Buchner funnel by vacuum filtration. ‘Wash it with water (~2 mL) and allow it to air dry until the next period. ‘Add 10 mL of saturated sodium chloride solution to the ether remaining in the separatory funnel and shake gently. Allow the layers to separate and discard the lower sodium chloride layer. Pour the ether layer into a beaker containing 1 g of anhydrous NaySO, and allow it to stand for about 15 minutes. Decant the ether into a 25 mL Erlenmeyer flask and evaporate by using a stream of air directed into the flask (connect ‘amber tubing to your air line and at the open end, insert a pipet as in figure 7.17A of p 612 of PLKE). ‘When all of the ether has evaporated, weigh the remaining solid (note: if an oil forms instead of a solid, just let it cool on ice until it solidifies). ulReerystallization of the neutral compound: The solid isolated from the ether layer will undergo a sem: microscale recrystallization in an Erlenmeyer flask (see section 11.3). The solvent of choice is hexane. Follow the procedure below: Place your solid in a 10 mL Erlenmeyer flask, add an appropriate amount of hot hexane and heat on a steam bath until the sample dissolves. If necessary, add more hexane, dropwise, until all the solid dissolves. Once dissolved, set the solution aside and let it cool to room temperature. Once at room temperature, cool the solution on an ice bath until crystal formation is complete. Filter the crystals on a Buchner funnel and wash with cold hexane (approx 0.5 mL). Identification of the components in the original mixture: Weigh and take melting points for the 3 isolated compounds. If the compounds are not yet dry, melting points can be taken during the next lab period. The melting points values are: Benzoic acid—122 °C Toluic acid—110 °C 4-(dimethylamino)benzaldehyde ~ 74 °C Ethyl 4-aminobenzoate — 94 °C Dibromobenzene ~ 89 °C Benzophenone — 50°C Waste Disposal: All aqueous acid and basic waste goes into the Aqueous Acid/Basic waste jug located in the hood. Ether goes into the Organic Solvent Waste (Do not put aqueous solutions in this!!). There is also a jug for solid waste (sodium sulfate & organic solids) Do not put filter paper, cotton, ete into the solid waste jug—the trash is fine. 2