Ninie Husen Wednesday, February 09, 2011

Experiment: 3Separation of a Mixture of Organic Compounds by Liquid-liquid Extraction Objective: The object of the experiment was to isolate samples of crude phenanthrene, m-toluic acid and p-chloroaniline from a stock solution through the process of liquid-liquid extraction as well recrystallization of the crude Phenathrene through the process of mixed solvent. The Melting range, solubility and thin layer chromatography tests were carried on the isolated products to evaluate the purity of the compounds.

Chemical Equations:

Figure1: The Extraction of M-toluic acid from an organic solvent by use of aqueous sodium hydroxide

Figure 2: the extraction of P-chloroanilinefrom an organic solvent by use of Aqueous chydrochloric acid Note:Phenanthrene was also involve in the reaction , but did not undergo any chemical change. Phenethrene aromatic hydrocarbon, which lack reactive group, hence It is exceptional stable and do not react with basic and acid under normal condition( Marrs, 2011)

Procedure: Refer to Chem 235 Lab Manual.

Reagents and Products: Table 1: Reagents of the Separation of a Mixture of Organic Compounds by Liquidliquid Extraction1 Compound MW Used Mole Physical and Safety Data (g/mole) Stock solution (p1g/100mL 100 mL See See products table for chloroaniline(1g/100ml), m-Toluic products individual physical and acid(1g/100ml), table for safety data properties. Phenanthrene(2g/100ml) individual moles Dichloromethane, CH2Cl2 84.93 0.5 mL Solvent d 1.325 g/mL, cancer suspect agent, irritant. Dispose as halogenated waste. 3M Sodium Hydroxide, NaOH 40.00 3 x 30 4.8 d 2.13 g/mL, corrosive, mL toxic. Dispose in basic aqueous waste container. 3M Hydrochloric Acid, HCl 36.46 3 x 30 4.986 d 2.02 g/mL. Highly mL toxic, corrosive. Dispose as acidic aqueous waste. Sodium Sulfate, anhydrous, NaSO4 142.04 4.5 g 0.032 d 2.68 g/mL, hygroscopic. Wrap securely and dispose in landfill waste. Ethanol, C2H5OH 46.07 23mL Solvent bp 78C, d 0.790 g/mL, flammable liquid, irritant. Dispose as non halogenated waste. Hexanes, C6H14 86.18 3ml Solvent bp 68-70C, d 0.672 g/mL, flammable liquid, irritant. Dispose as non halogenated waste. Toluene, 92.14 3ml Solvent Flammable liquid, toxic. C6H5CH3 Dispose as nonhalogenated waste. Water, H2O 18.02 3ml Solvent d 1.0 g/mL, solvent. Cyclohexane, C6H12 84.16 2ml Solvent Mp 6.5C, Bp 80.7C, d 0.779g/mol.flammable, Dispose as nonhalogenated waste Bp 77C ,d0.902g/ml, flammable liquid

Ethyl acetate, CH3CO2C2H5

88.11

1ml

Solvent

p-anisaldehydeCH3OC6H4COH

136.15

Stain

Dispose as nonhalogenated waste 3 Bp 248C, 1.119g/cm ,

clear to slight yellow Hazardous in case of ingestion, skin contact , and eye irritant.suspectedof neurotoxin

bromocresol green, C21H14Br4O5S

698.01

Stain

d 0.799g/ml irritant to eye and skin[2].

Table 2: Products of the Separation of a Mixture of Organic Compounds by Liquid-liquid Extraction1,2

Compound

Crude Phenanthrene, C14H10

MW (g/mol e) 178.23

Isolated

Moles

Yield

Physical and Safety Data1

2.00 g

0.0112

100%

RecrystallizedPh enanthrene, C14H10

178.23

0.80 g

0.004

80%

p-chloroaniline, BrC6H4NH2

172.02

0.80g

0.005

80%

m-Toluic acid, CH3C6H4CO2H

136.15

1.3 g

0.009

130%

d 2.0 g/mL, harmful if swallowed, inhaled or absorbed through the skin, irritantto the eyes ,the respiratory system, and skin. d 2.0 g/mL, harmful if swallowed, inhaled or absorbed through the skin, irritantto the eye, the respiratory system, and skin. d 1.0 g/mL at 25 C, toxicby inhalation, in contact with skin and if swallowed. Wear suitable protective clothing and gloves. d 1.0 g/mL at 25 C, harmful if swallowed, irritant.

Experimental Data and Observations: Table 3: Observed solubility of recrystallizedPhenanthrene, m-Toluic acid, and Anthranilic acid1 Compound Phenanthrene m-Toluic acid Anthranilic acid Ethanol Cold Hot v v v s v Hexanes Cold Hot s v i i Toluene Cold Hot v v v i v Water Cold Hot i i i s

Note:Very soluble (v): 40mg of solute dissolves in 0.5mL of solvent1 Soluble(s): 20mg of solute dissolves in 0.5ml of solvent1 Slightlysoluble( ): Some of the 20mg solvent will dissolve in 0.5mL of solvent1 Insoluble (i): None of the solute appears to dissolve1 Table 4: Observed and Actual Melting Point Ranges of m-Toluic acid, p-chloroaniline, Crude Phenanthrene and RecrystallizedPhenanthrene

Compound

Observed Melting point range (oC)

Crude Phenanthrene 90-95 RecrystallizedPhenanthrene 99-100 m-Toluic acid p-chloroaniline 107-111 74-76

Actual melting point Range (o C) 99-101 99-101 107-113 74-76

Inference impurity level Some impurities Negligible impurity Some impurity Some impurity

Table 5hh:Thin layer chromatography Plate Analysis of crude and recrystallizedphenanthrene and stock solution. Compound Crude phenanthrene Distance travelled 2.3 Rf value 0.53 0.56 0.54 TLC parameters Plate used (stationary phase) 6.5 cm strip of Silica gel chromatographyplate Solvent used (mobile phase) 2:1 mixture of cyclohexane and ethyl acetate with depth of 1 cm Observed under UV light

Recrystallizedphenanthrene 2.5 Stock solution phenanthrene 2.4

M-toluic acid P-chloroanilline

1.6 0.85

0.36 0.19

Solvent front = 4.45 Stained used: p-anisaldehyde stain and bromocresol green stain

CR: Crude Phenanthrene RR: RecrystallizedPhenanthrene SS: Stock solution dph distance treveled by phenanthrene dm distance traveled by M-toluic acid dp distance traveled by p-choloroaniline ds distance moved by solvent front

ds

ds

Figure 3: Thin layer chromatography sheet a and b stained with P-anisaldehydeand Bromocresol Green in that order.

Calculations: Moles Crude Phenanthrene: 2.00 g x = 0.0112 moles Crude Phenanthrene 1 178.23 g/mol

Percent Yield by mass of crude Phenanthrene: Theoretical yield = (concetration by mass) x (volume used) = (2 g/100ml) x (100ml) = 2.00 g Percentage Yield = (mass experimental yield/mass of theoretical yield) x 100 % = 2.00 g/ 2.00g x100% = 100% Percent Yield by mass ofrecrystallizedPhenanthrene

Mass Yielded (g) / Mass Used (g) x 100% = 0.80g /1.0 g x 100% = 80% recrystallizedphenanthrene Percent Yield by mass ofp-chloroaniline Theoretical yield = (concetration by mass) x (volume used) = ( 1 g/100ml) x (100ml) = 1.00 g Percentage Yield = (mass experimental yield/mass of theoretical yield) x 100 % = 0.80g/ 1.00g x100% = 80%

Percent Yield by mass of M-toluic acid Theoretical yield = (concetration by mass) x (volume used) = ( 1g/100ml) x (100ml) = 1.00 g Percentage Yield = (mass experimental yield/mass of theoretical yield) x 100 % = 1.3g/ 1.00g x100% = 130% Rfvalues: The distance compound centre moved from origin(cm)/ distance traveled by solvent front(cm) Calculationof Crude Phenanthrene (No Units): Distance traveled by compound (cm) / Distance traveled by solvent front (cm) = 2.3 cm/4.45 cm = 0.53 Calculationof RecrystallizedPhenanthrene (No Units) = 2.5 cm/4.45 cm = 0.56 Calculationof Stock solutionPhenanthrene (No Units) = 2.4 cm/4.45 cm = 0.54 Calculationof M-toluic acid (No Units) = 1.6 cm/4.45 cm = 0.36

Calculationof p-chloroaniline(No Units) = 0.85 cm/4.45 cm = 0.53

Discussion: The percent yields by mass percents were determined to be 130%, 80% and 100% for mtoluic acid, p-chloroaniline, and crude phenanthrene respectively. The fairly high percent yield of m-toluic acid indicated that there were some impurities in the sample On the other hand , the the relatively fair percent yield of crude phenanthrene , recrystallizedphenanthrene and p-chloroanillinedemonstrated minimal impurities in the sample The observed melting range of the crude phenethrene was 90- 95 oC , which was some lower than the melting range 99 101 oC given by the literature (Marrs, 20111). The Rf value of the crude phenanthrene obtained from thin layer chromatography test was 0.52, which was slightly lower than the Rf value given by the Phenanthrene component of the stock solution, which was 0.54. The absence of the yellow spot on the of crude phenanthrene ,when the plate was immersed in the Bromocresol green and Panisaldehyde, indicated that the crude phenanthrene was pure of the m-toluic acid and pchloroaniline. It was concluded that the crude phenanthrene had some impurities The observed melting of the recrystallizedphenanthrene was 99-100 oC, which was nearly the same with the melting range 99-101oC given by the literature(Marrs, 20111). The Rf value of this recrystallized sample was 0.56, which was some how higher than the Rf value obtained from the phenanthrene component of the stock solution as above. The absence of the yellow spot on the crude phenanthrene,when the plate was immersed in the Bromocresol green and P-anisaldehyde, indicated that the crude phenanthrene was pure of the m-toluic acid and p-chloroaniline.Nevertheless, there were some unexplained spot on both crude and recrystallizedphenethrene plate, which attributed to impurities .It had been concluded that the recrystallized phenanthrenenhad slight impurities. The obtained melting range of the M-Toluic acid was 107-111oC, which was in the melting range reported by Literature( Marrs, 20111), that was 107-113oC. Even though, the melting range was in the melting range of literature, the M- toluic acid had some impurity.The Rf value of the M Toluic acid was 0.36, which calculated from the stock solution component when the bromocresol green stain indicated yellow spot on the stock solution and the M toluic acid is very soluble in both hot and cold ethanol. The obtained melting range of the p-chloroaniline was 74-76oC, which was sightly higher than the melting range reported by Literature (Marrs, 20111), which was 72-73oC..The Rf value of was 0.19 which calculated from the stock solution component when the Panisaldehyde indicated yellow spot on the stock solution.From the melting range stand point , the sample of the P-chloroaniline had some impurities

The solubility test showed that m-toluicacid ,anthranilic, and recrystallizedphenanthrene were very soluble in hot ethanol as tabulated in table Moreover ,the recrystallized phenanthrene was insoluble in both cold and hot water, while the m-toluic acid was insoluble in cold and soluble in hot water. The anthranilic was slightly soluble in cold water and soluble in hot water. The M-toluic acid was very soluble in hot toluene and slightly soluble in coldToluene, whereas anthranilic acid was insoluble in toluene at cold temperatures, but very soluble in hot toluene. Therefore, a sample ofm-toluic acid and anthranilic acid put in a solution of hot toluene would result in both of the compounds dissolving. By cooling the toluene, it would be possible to recrystallize the anthranilic acid out of the solution and isolate it. Then with the addition of cold water to the cold toluene solution the recrystallization of m-toluic acid would occur due to the observed insolubility of m-toluic acid in the cold water. Thus,the solubility data revealed that a mixed solvent system of toluene and water would be best for the recrystallization of mtoluic and anthranilic acid separately.

References: 1. P. Marrs, Chem lab Manual, pp.45-50. (University of Victoria: Victoria, BC). 2011. 2. Sigma Aldrich website www.sigmaaldrich.com