Experiment #2 – Part 1 Adam Capriola

10/17/07 Dr. Murray

“Acid/Base Extraction” Lab Partner: David Lemon

I. Introduction

A. Objective

The purpose of this experiment is to separate a prepared mixture of benzoic acid, 4-

nitroaniline, and naphthalene by the technique of extraction. The compounds will be extracted

on the basis of the solubility properties of the acids, bases, and their salts. The given unknown

sample will be dissolved with dichloromethane. Hydrochloric acid will then be added and

extraction of p-nitroaniline will be performed in two steps: mixing and separation. The extracted

p-nitroaniline will then be isolated by adding aqueous sodium hydroxide which will turn the

solution basic which will cause the p-nitroaniline to precipitate. The benzoic acid will be

extracted by adding sodium hydroxide to the dichloromethane solution and using the process of

separation. The benzoic acid will then be isolated using aqueous hydrochloric acid to turn the

solution acidic which will make the benzoic acid precipitate. These two precipitates will be

collected using vacuum filtration. The 4-nitroaniline will be recrystallized using boiling water,

and will then be weighed and measured for its melting point. The benzoic acid will also be

recrystallized using boiling water, and will then be weighed and measured for its melting point.

Anhydrous sodium sulfate will be added to the left over dichloromethane solution. The mixture

will react and then be filtered, and the solid residue of naphthalene will be weighed.

B. Materials and Safety

Chemical Name Molecular Molecular Liquid Solid Solubility Potential
Formula Weight Hazards
(g/mol) b.p. Density m.p.
ºC g/mL ºC
Hydrochloric HCl 36.46 48 -- −26 H2O Corrosive
Acid
Sodium NaOH 40.0 1390 2.130 318.4 H2O Causes
Hydroxide burns
Sodium Sulfate Na2SO4 142.04 -- -- 241 H2O Irritant
Benzoic Acid C7H6O2 122.12 249.2 1.2659 122.4 H2O 2; Safe, found
EtOH 3; in foods
eth 3; ace
3
Naphthalene C10H8 128.17 217.9 1.0253 80.2 H2O 2; Carcinogen
EtOH 3;
eth 3; ace
4
Dichloromethane CH2Cl2 84.93 39 1.3255 -96.7 H2O Slightly
toxic
4-Nitroaniline C6H6N2O2 138.12 260 1.437 146- H2O Toxic
149

C. Experimental Procedure

A prepared mixture of unknown relative amounts benzoic acid, 4-nitroaniline, and

naphthalene will first be obtained. The weight of the mixture will be taken and recorded. The

sample will then be transferred to a 15 mL glass centrifuge tube. 3.0 mL of dichloromethane

will then be added to the tube and the mixture will be dissolved by shaking the tube gently.

Next, 1.5 mL of 6 M aqueous hydrochloric acid will be added to the centrifuge tube. The

mixture will be mixed by capping the tube and shaking it by hand to thoroughly mix the two

phases. The centrifuge tube will then be vented by loosening the cap, and then it will be clamped

to allow the two phases to separate. The dichloromethane layer will be separated using a pipet

with bulb on top. The dichloromethane layer will be sucked into the pipet and transferred to a

reaction tube. The left over aqueous layer will be transferred into a 20 x 80 mm vial labeled

“aqueous acid extracts” in the same manner using a new pipet. The dichloromethane layer will
then be transferred back to the centrifuge tube using a pipet. This technique will be repeated by

adding another 1.5 mL of 6 M aqueous hydrochloric acid to the centrifuge tube as before.

Next, 1.5 mL of cold 3 M sodium hydroxide solution will be added to the centrifuge tube

with dichloromethane. The same procedure will be followed as above for mixing and separating,

except this time the aqueous layer will be transferred to a 20 x 80 mm vial labeled “aqueous

hydroxide extracts”.

After that, 12 M aqueous hydrochloric acid will be added to the 20 x 80 mm vial labeled

“aqueous hydroxide extracts” dropwise until the solution is acidic. The vial will be placed in an

ice bath while this takes place. Next, 6 M aqueous sodium hydroxide will be added dropwise to

the vial labeled “aqueous acid extracts” until the solution is basic. This will also take place in an

ice bath. The solid formed by these steps will be separately filtered via vacuum filtration using a

25 mL filter flask. The precipitates, benzoic acid and p-nitroaniline, will be transferred to filter

paper and allowed to dry, then will be weighed. If specified, 4-nitroaniline and benzoic acid will

be recrystallized from boiling water. These samples would then be dried, weighed, and have

their melting points determined.

The dichloromethane solution will then be dried by adding about 0.3 g of anhydrous

sodium sulfate to the centrifuge tube. The tube will be briefly shaken and allowed to stand for 5

minutes with occasional swirling. Finally, the dichloromethane solution will be filtered or

decanted into a tared reaction tube under the hood. The weight of the solid residue in the

reaction tube will be determined and the tube will be stoppered. If specified, the solid residue

will be purified by column chromatography.

II. Experiment and Results

 A. Data

A sample comprised of a mixture of unknown proportions of benzoic acid, 4-nitroaniline

(p-nitroaniline), and naphthalene weighing 0.292 g was obtained. The sample was transferred

into a 15 mL glass centrifuge tube along with 3.0 mL of dichloromethane. The mixture was

dissolved by gently shaking the tube. Once the mixture was completely dissolved, 1.5 mL of 6

M aqueous hydrochloric acid was added to the centrifuge tube. The tube was capped and shaken

to thoroughly mix the two phases. The tube was then uncapped and clamped vertically to a ring

stand. A pipet was then used to take a sample of the upper layer of the mixture, which was then

put into a separate clean centrifuge tube. An equal amount of water was then put into this test

tube to confirm that the upper layer was the aqueous layer. The contents in the second tube were

then transferred back into the original tube using the pipet.

The lower layer of the mixture, the dichloromethane layer, was then transferred using the

pipet into a clean centrifuge tube. The remaining aqueous layer was transferred using the pipet

into a separate clean tube labeled “aqueous acid extracts”. The dichloromethane layer was then

transferred back to the original centrifuge tube again using the pipet. Another 1.5 mL of 6 M

aqueous hydrochloric acid was added to the tube with dichloromethane and the process of

separating the two layers was performed for a second time. The aqueous layer was transferred to

the same test tube as before containing aqueous acid extracts.

Next, 1.5 mL of cold 3 M sodium hydroxide solution was added to the centrifuge tube

containing dichloromethane. The tube was capped and shaken to thoroughly mix the two phases,

just as before. The dichloromethane layer was again separated from the aqueous layer, and this

time the aqueous solution was transferred into a clean centrifuge tube labeled “aqueous
hydroxide extracts”. This process was repeated a second time by adding an additional 1.5 mL of

cold 3 M sodium hydroxide solution to the dichloromethane solution.

After that, about 0.3 g of anhydrous sodium sulfate was added to the left over

dichloromethane layer remaining in the centrifuge tube. The tube was shaken allowed to stand

with occasional swirling. While the tube was allowed to stand, the tube containing aqueous

hydroxide extracts was placed into an ice bath and 12 M aqueous hydrochloric acid was added

dropwise to the until the solution turned acidic. A precipitate, benzoic acid, formed which was

filtered out via vacuum filtration. The benzoic acid was allowed to air dry for a week. It was

then weighed at 0.074 g and its melting point was about 119 ºC.

The tube labeled “aqueous acid extracts” was also placed in an ice bath and 6 M aqueous

sodium hydroxide was added to the solution until the solution turned basic. A precipitate, p-

nitroaniline, formed which was also filtered via vacuum filtration. The p-nitroaniline was

allowed to air dry for a week. The resulting p-nitroaniline was weighed at 0.040 g and its

melting point was about 139 ºC. The dichloromethane solution which was allowed to stand was

decanted into a clean test tube. The solvent was then removed under a stream of nitrogen in the

hood. The solid residue, naphthalene, was allowed to air dry for a week. The naphthalene was

weighed at 0.035 g and its melting point was 76 ºC.

Sample Weight (g) 0.292

Weight of Benzoic Acid (g) 0.074
Melting Point of Benzoic Acid (ºC) 119
Weight of p-nitroaniline (g) 0.040
Melting Point of p-nitroaniline (ºC) 139
Weight of Naphthalene (g) 0.035 g
Melting Point of Naphthalene (ºC) 76

III. Conclusions
 The compounds extracted seem to be slightly impure. The melting points for benzoic

acid, p-nitroaniline, and naphthalene that were found are all slightly lower than the melting

points I looked up beforehand. There are not huge discrepancies in the numbers, so this leads me

to believe the compounds extracted are the expected compounds, they are just not completely

pure, which is to be expected.

Error in this experiment could have come from a few different sources. One step that

could have led to error was during separation. It was hard to extract only the dichloromethane

layer, so I am sure some of the aqueous layer was picked up with it. This means that the

resulting aqueous solution, whether it be acid or hydroxide extracts, would yield slightly less

benzoic acid and p-nitroaniline than expected. If the error were to happen the other way around

and some of the dichloromethane layer was picked up with the aqueous extracts, which means

less naphthalene would have resulted than expected. It was impossible to be precise with the

separation, so that means there was going to be error in the final weight either way.

If the 3 M sodium hydroxide added during separation was not cold, I think the benzoic

acid would not have been as soluble in the aqueous solution and therefore less benzoic acid

would have resulted than expected. A couple other obvious spots where error occurred were

during vacuum filtration and decanting of the dichloromethane. Some filtrate could have been

lost if it were too close to the edge of the filter paper. During the decanting of dichloromethane,

some of the liquid may not have made it would of the tube. Lastly, I know it was hard to get all

of the naphthalene out of tube to weigh it, so the weight of naphthalene recovered is low.