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Acid and Base Extraction

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Acid and Base Extraction
Finding the unknown compound by extraction using their conjugate acid and base.

Huda

Introduction
The purpose of the acid and base extraction lab is to determine the unknown mixture that contains three compounds which is made of an organic acid, an organic base and an organic neutral. To find out what the unknown compounds are found in the mixture, a series of techniques are done. To extract the compounds from the given unknown mixture, they were changed back to their conjugate acids by adding a strong acid and back to their conjugate bases by adding a strong base.
The first technique is called extraction in which organic Bases and organic acids are separated from neutral compounds and from each other by using an aqueous solution of different PH values. Compounds that contain less than six carbons are not affected by changing the pH value. The compounds are extracted based on the solubility properties of the acid, bases and salts. The unknown compound will be dissolved in dichloromethane and HCl will be added and extraction will occur by mixing the solution and removing the aqueous layer. The extracted aqueous layer will be isolated by adding NaOH which will make the solution basic that will lead it to precipitate. The organic acid will be extracted NaOH to the dichloromethane solution and separating the aqueous solution. The majority of organic carboxylic acids are highly soluble in dilute NaOH since the acid gets deprotonated by the base and are slightly soluble or insoluble in H2O.
The carboxylic acids are isolated by the dissolving the unknown mixture in a solvent that’s immiscible with H2O then extracting the solution with NaOH. The aqueous basic solution is acidified. Then the acid will precipitate from the solution. Organic bases that are insoluble in H2O can be separated by using the extraction method with HCl. This will produce ammonium salt that is soluble in H2O and not in organic solvents. The amine is recovered from the aqueous solution by adding a base. This will convert the ammonium salt back to the amine which will precipitate.
The second technique is recrystallization. In which the solution is placed in a Hirsch funnel with a filter paper and suction filtration is performed. Water was used to wash out the solution during filtration. The crystals were set aside to dry on a paper towel. The third technique is measuring the melting point by three different ramp rate ranging at 0.5, 10 and 20. The starting temperature was started 20 degrees below the predicted melting point. After measuring the melting point for each of the acid, base and the neutral compounds, I had to compare the range of the unknown melting point to the range of the known melting points. If there are no to little impurities in the crystals then the melting point of the unknown compound should be in the range of the known compounds listed. Trying to minimize the amount of impurities in the crystals will produce an accurate or in the range of the melting points given. Materials
Unknown #77
5 ml Dichloromethane
5% Hydrochloric acid
5% HCl
5% NaOH
10% NaOH
10% HCl
.10g anhydrous sodium sulfate (Na2SO4)
H2O
Filtration (Hirsch funnel, filter paper, Buchner flask and a vacuum.)
Ice bath (beaker and ice)
Litmus paper
Stirring rod
3 test tubes and a rack
Corks
Pasteur pipet
Spatula
Capillary tubes
Melting point apparatus

Procedure
Part A.
An unknown sample that weighed .72g was transferred to a 20ml test tube and dissolved in 5.0ml of dichloromethane. The dichloromethane solution was extracted with 2.5 mL of 5% hydrochloric acid by adding the hydrochloric acid to the sample in the test tube. The test tube was shaken for two minutes. The test tube was left to stand until the layers separated and opened carefully. A Pasteur pipet was used to separate the layers. The top layer was the aqueous layer and was placed in a test tube labeled ‘HCl extract’. The dichloromethane layer was extracted with another 2.5 mL portion of 5% HCl and combined the second HCl extract with the original. The combined HCl extract was mixed and tested with litmus paper to be sure that they were acidic. 2.5mL of H2O was added to the dichloromethane solution and the water was added to wash the HCl extract and was set aside for part B. The dichloromethane solution was extracted with 2.5 mL of 5% NaOH. The aqueous layer was placed in a test tube labled ‘NaOH extract’. The dichloromethane layer was extracted with another 2.5 mL portion of 5% NaOH and combined the second NaOH extract with the original. The combined NaOH extract was mixed and tested with litmus paper to be sure they were basic. The dichloromethane layer was washed with 2.5 mL of water, and water was added to the NaOH extract and set the NaOH extract for part B. 0.10g anhydrous sodium sulfate was added to the dichloromethane solution. The weight of the test tube was measured. The dichloromethane solution was transferred to it. The original test tube was rinsed with a small amount of dichloromethane and combined with the solution in the pre-weighed test tube.

Part B. 1. Basic Fraction from HCl
The HCl extract was cooled in an ice bath. 4 mL of 10% NaOH solution was added in a test tube and added it drop wise to the cooled HCl extract while it was stirred, until the solution became basic. The sides of the test tube were scratched by using a stirring rod to facilitate precipitation. The liquid was separated from the solid by suction filtration. The solid was washed twice with cold water. The filter paper was placed on paper towel and let the product dry. The weight and MP of the dried product was determined 2. Acidic Fraction from NaOH Extraction
The NaOH extract was cooled in an ice bath. 1 mL of 10% HCl solution was added in a test tube and added it drop wise to the cooled NaOH extract while it was stirred, until the solution became basic. The sides of the test tube were scratched by using a stirring rod to facilitate precipitation. The liquid was separated from the solid by suction filtration. The solid was washed twice with cold water. The filter paper was placed on paper towel and let the product dry. The weight and MP of the dried product was determined 3. Neutral Fraction
The dichloromethane was evaporated by leaving the test tube uncovered. The test tube and the product were weighed by difference. The MP of the dried product was calculated.

Reagent/Reactant | Amount | Molecular Weight | Bp | Mp | Density | 5-Chloro-2-methoxyaniline | .33g | 157.60 g/mol1 | 135 °C1 | 81-83 °C1 | ------ | Biphenyl | .62g | 154.21 g/mol2 | 256°C2 | 69-70oC2 | 1.042 | Cinnamic | .35g | 148.16 g/mol3 | 300oC3 | 132-135oC3 | 1.253 | Dichloromethane | 5ml | 84.93 g/mol4 | 39.8-40.0oC4 | -97oC4 | 1.325 g/ml4 |

Data Unknown mixture | .72g | HCl extract weight | .33g | NaOH extract weight | .35g | Neutral fraction weight | .62g | NaOH mp at 0.5 ramp rate | 131.8-132.9oC | NaOH mp at 10 ramp rate | 133.9-134.7 oC | NaOH mp at 20 ramp rate | 134.5-136.7 oC | Neutral fraction mp at 0.5 ramp rate | 61.4-62.3 oC | Neutral fraction mp at 10 ramp rate | 62.6-63.5 oC | Neutral fraction mp at 0.5 ramp rate | 64.2-67.6 oC | HCl mp at 0.5 ramp rate | 82.5-82.7 oC | HCl mp at 10 ramp rate | 83.5-85.2 oC | HCl mp at 20 ramp rate | 84.6-86.1 oC |

Results
Percentage yield of the Organic Base= (.33g/.72g)x100=45.83%
Percentage yield of the Organic Acid= (.35g/.72g)x100=48.61%
Percentage yield of the Neutral Fraction= (.62g/.72g)x100=86.11%
Organic Base= 5-Chloro-2-Methoxyanaline with a melting point of 83-85oC
Organic Acid= Cinnamic with a melting point of 132oC
Neutral Fraction= Biphenyl with a melting point range of 65oC

After measuring the melting points of the each compound, it shows that each of the organic base and organic acid were in the range of the known melting points listed. The neutral fractions melting point was off by 4 degrees, this indicates that impurities were found in the final product of the crystals.
Discussion and Analysis
Based on the hypothesis made that if there are no to little impurities in the crystals then the melting point of the unknown compound should be in the range of the known compounds listed, is correct based on the range of the melting points measured. Performing this lab experiment is important not to have any impurities in the crystals to get an accurate result and reading of the melting point.
One of the problems occurred during the lab experiment is that I forgot to take off the cork from the neutral fraction test tube. This led to the dichloromethane solution to remain in the test tube and not evaporate. I followed the instructions on how to evaporate the dichloromethane by warming the test tube by placing it in the hot bath at 50oC for more than an hour but no amount of the dichloromethane evaporated. Then I removed the test tube from the hot bath and left it in the drawer uncovered over the weekend to let the dichloromethane evaporate.
The second problem occurred during the lab experiment is when I performed the recrystallization technique. After separating the crystals using the filtrating apparatus I didn’t let the crystals to dry completely because of the timing. So when I took the melting point of the semi dry neutral fraction crystals, it gave me a broad range. It didn’t match any of the known melting points listed. I had to leave it over the weekend to let it completely dry and took the melting point again and gave me a better result.
While taking the melting points for each of the unknown compounds, it is recommended to measure three melting points at different ramp rates ranging from 0.5,10 and 20 for the each product. It is preferable to start 20 degrees below the approximate melting point listed. I learned to get three melting points for a better result compared to the melting points taken during the recrystallization experiment, were I only took the 20 ramp rate and gave a broad melting point range.
The melting points measured for the organic acid also known as Cinnamic was (131.8-132.9oC) which is close to the listed melting point measured at 132oC. The organic base known as 5-Chloro-2-Methoxyanaline was measured at (83.5-85.2oC) that’s in the range of the listed melting point measured at 83-85oC. The neutral fraction known as Biphenyl was off by four degrees from the listed melting point. The melting point measured was 64.2-67.6oC compared to the listed melting point at 69-72oC. This indicated that small amounts of impurities were present in the crystals formed. I had two choices to find out what my unknown is since none of the knowns matched the melting point that I measured. The two choices were 2-chloroacetophenone with a melting point range of 54-56oC and Biphenyl. I figured that Biphenyl was my third unknown compound since the range that I measured was the closest to the listed Biphenyl melting point by four degrees compared to the 2-chloroacetophenone that was eight degrees away.
Conclusion

The compounds that were extracted seemed to have small amounts of impurities since the melting point of the unknown compounds weren’t exactly as the known compounds melting point. The melting points for 5-Chloro-2-methoxyaniline, Biphenyl and Cinnamic that were found are all in the range of the melting points that were listed. This makes my hypothesis true that if there are no to little impurities in the crystals then the melting point of the unknown compound should be in the range of the known compounds listed. I learned that Cinammic is highly soluble in HCl until its deprotonated and gets soluble in water. The acid or base doesn’t have an effect on the solubility of biphenyl because it doesn’t contain functional groups that will change by adding or removing a proton.

References 1. 95-03-4(5-Chloro-2-methoxyaniline) Product Description. 95-03-4 CAS MSDS (5-Chloro-2-methoxyaniline) Melting Point Boiling Point Density CAS Chemical Properties, http://www.chemicalbook.com/chemicalproductproperty_us_cb5854691.aspx, (accessed December 10, 2015). 2. Biphenyl. Biphenyl, http://pubchem.ncbi.nlm.nih.gov/compound/biphenyl#section=top (accessed December 10, 2015). 3. CINNAMIC ACID. CINNAMIC ACID, http://pubchem.ncbi.nlm.nih.gov/compound/444539#section=top (accessed December 10, 2015). 4. Dichloromethane - High Purity Solvents. Sigma-Aldrich, http://www.sigmaaldrich.com/chemistry/solvents/dichloromethane-center.html (accessed December 10, 2015).

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