Experimental organic chemistry (Extraction)

Extraction

Extraction is a technique commonly used in organic chemistry to separate a

material you want from those you do not. While the term extraction may be unfamiliar

to you, the process is actually something you commonly perform. For example,

many of you probably start the day, especially after a long night of studying, with an

extraction when you brew a pot of coffee or tea. By heating coffee grounds or tea

leaves with hot water, you extract the caffeine, together with other water-soluble

compounds such as dark-colored tannins, from the solid material. You can then

drink the liquid, which is certainly more enjoyable than eating coffee grounds or tea

leaves, to ingest the caffeine and benefit from its stimulating effect. Similarly, when

you make a soup, the largely aqueous liquid portion contains numerous organic

and inorganic compounds that have been extracted from spices, vegetables, fish,

or meat, and these give your culinary creation its distinctive flavor. In the procedures

found in this chapter, you will have an opportunity to develop your existing experimen-

tal skills further by isolating organic compounds using different types of extractions.

5.1 I N T R O D U C T I O N

The desired compound from a reaction is frequently part of a mixture, and its isolation in pure form can be a significant experimental challenge. Two of the morecommon methods for separating and purifying organic liquids and solids arerecrystallization and distillation; these procedures are discussed in Chapters 3and 4, respectively. Two other important techniques available for these purposesare extraction and chromatography. As you will see here and in Chapter 6, both of these methods involve partitioning of compounds between two immiscible

phases. This process is termed phase distribution and can result in separation ofcompounds if they distribute differently between the two phases.

Distribution of solutes between phases is the result of partitioning or adsorption

phenomena. Partitioning involves the difference in solubilities of a substance in twoimmiscible solvents—in other words, selective dissolution. Adsorption, on the otherhand, is based on the selective attraction of a substance in a liquid or gaseous mixture tothe surface of a solid phase. The various chromatographic techniques depend on bothof these processes, whereas the process of extraction relies only on partitioning.

Extraction involves selectively removing one or more components of a solid,liquid, or gaseous mixture into a separate phase. The substance being extractedwill partition between the two immiscible phases that are in contact, and the ratioof its distribution between the phases will depend on the relative solubility of thesolute in each phase.

153

C H A P T E R5

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5.2 T H E O R Y O F E X T R A C T I O N

Liquid-liquid extraction is one of the most common methods for removing anorganic compound from a mixture. This process is used by chemists not only in theisolation of natural products but also in the isolation and purification of productsfrom most chemical reactions.

The technique involves distributing a solute, A, between two immiscible liquids,Sx, the extracting phase, and So, the original phase. The immiscible liquids normallyencountered in the organic laboratory are water and some organic solvent, such asdiethyl ether, (C2H5)2O, or dichloromethane, CH2Cl2. At a given temperature, theamount of A, in g/mL, in each phase is expressed quantitatively in terms of a constant,K, commonly called the partition coefficient (Eq. 5.1). Strictly speaking, the volumesof solution should be used in the definition of [A], but if the solutions are dilute, onlyslight errors result if volumes of solvent are used. Furthermore, a close approximation

of the partition coefficient K may be obtained by simply dividing the solubility of A inthe extracting solvent Sx by the solubility of A in the original solvent So.

(5.1)

The process of liquid-liquid extraction can be considered a competitionbetween two immiscible liquids for solute A, with solute A distributing or parti-tioning between these two liquids when it is in contact with both of them. Themathematical expression of Equation 5.1 shows that at equilibrium, the ratio of con-centrations of A in the two phases will always be constant.

Equation 5.1 leads to several important predictions. For example, if K > 1, soluteA will be mainly in the extracting solvent, Sx, so long as the volume, Vx, of this solventis at least equal to the volume, Vo, of the original solvent So; the amount of soluteremaining in So will depend on the value of K. By recasting Equation 5.1 into Equation 5.2, it is easily seen that if the volumes of Sx and So are equal, the value of Kis simply the ratio of the grams of A in each solvent. Because the product of the ratiosAx/Ao and Vo/Vx must be constant for a given solvent pair, increasing the volume ofextracting solvent Sx will result in a net increase in the amount of solute A in Sx.

(5.2)

There are practical, economic, and environmental reasons, however, that limitthe quantities of organic solvents that can realistically be used in extractions. Thequestion thus arises as to whether it is better to perform a single extraction with all of the solvent, or to perform several extractions with smaller volumes. For example, if an organic compound is dissolved in 10 mL of water, and only 30 mL ofdiethyl ether is used, will three extractions with 10-mL portions of ether providebetter recovery of solute than a single one with 30 mL?

Applying Equation 5.2 would provide the answer, but the process is tedious formultiple extractions. This equation can be generalized, however, to accommodatemultiple extractions in terms of the fraction, FA, of solute A remaining in the originalsolvent So after n extractions, using a constant volume of an immiscible solvent Sxfor each extraction. Thus, the amount of solute remaining in So after one extractionwith Sx is obtained by rearranging Equation 5.3 to Equation 5.4. The fraction, FA, ofA still in the original solvent is obtained through Equation 5.5, in which Ci and Cf are the initial and final concentrations, respectively. For a second extraction,

K 5

grams of A in Sx

grams of A in So 3

mL of So

mL of Sx 5

Ax

Ao 3

Vo

Vx

K 5[A] in Sx

[A] in So

154 Experimental Organic Chemistry n Gilbert and Martin

Chapter 5 n Extraction 155

Equations 5.6–5.8 result. Equation 5.8 can be generalized to Equation 5.9 when nextractions are performed.

(5.3)

where Ao 5 amount (grams) of solute in So before extractionA1 5 (Ao – Ax) 5 amount (grams) of solute in So after extraction

Vo and Vx 5 volume (mL) of original and extracting solvents, respectively

(5.4)

(5.5)

where Ci 5 Ao/So and Cf 5 A1/So, respectively

(5.6)

(5.7)

(5.8)

(5.9)

Performing calculations according to Equation 5.9 for the case of K 5 5, weobtain FA 5 1/16 for a single extraction with 30 mL of diethyl ether, and 1/216 forthree extractions with 10-mL portions. This means that 6.3% of A remains in theaqueous phase when one extraction is performed, whereas the value drops to only0.5% in the case of three successive extractions with the same total volume of solvent. The amount of A that could be isolated is increased by some 6% with multiple extractions. Setting K at 2 gives corresponding values for FA of 1/7 and1/27, respectively, which translates to a 10% increase in the quantity of A that isremoved from the aqueous layer with multiple extractions.

From these calculations, it is clear that multiple extractions become increas-ingly important as the value of K decreases. The improved recovery of solute frommultiple extractions, though, must be balanced with the practical considerationthat the relatively small increase in recovery may not justify the additional timeand solvent required to perform multiple extractions unless the product is of greatvalue. Importantly, the partition coefficients K are generally large for the extrac-tions required in the procedures provided in this textbook, so only one or twoextractions are usually required.

Selection of the appropriate extracting solvent is obviously a key for successfullyusing this technique to isolate and purify compounds, and important guidelinesfor making the correct choice are summarized here.

1. The extracting solvent must not react in a chemically irreversible way with thecomponents of the mixture.

FA =

Cf

Ci= a Vo

KVx + Vobn

FA¿ =

Cf

Ci= a Vo

KVx + Vob2

K = Aoa Vo

KVx + Vob2

K = aA1 - A2

Vxb aVo

A2b

FA =

Cf

Ci=

Vo

KVx + Vo

A1 =(AoVo)

KVx + Vo

K 5 aAo - A1

Vxb aVo

A1b

2. The extracting solvent must be immiscible, or nearly so, with the original solution.

3. The extracting solvent must selectively remove the desired component from thesolution being extracted. That is, the partition coefficient K of the componentbeing removed must be high, while the partition coefficients of all other components should be low.

4. The extracting solvent should be readily separable from the solute. Use of avolatile solvent facilitates its removal by simple distillation or one of the othertechniques outlined in Section 2.29.

5.3 B A S E A N D A C I D E X T R A C T I O N S

The discussion of Section 5.2 focuses on partitioning one substance between two immiscible solvents. Now consider what happens if a mixture of two or more

compounds is present in a given volume of solvent So and an extraction using asolvent Sx is performed. If the partition coefficient K of one component, A, is signifi-

cantly greater than 1.0 and if those of other components are significantly less than1.0, the majority of A will be in Sx, whereas most of the other compounds willremain in S0. Physical separation of the two solvents will give a partial separation,and thus purification, of the solute A from the other components of the mixture.

Solutes differing significantly in polarity should have very different coeffi-cients K for partitioning between nonpolar and polar solvents. For example, con-sider the distribution of two organic compounds, the first neutral and nonpolar,and the second ionic and polar, between a nonpolar solvent and a polar solvent. Ifa solution of these compounds in the nonpolar solvent is shaken with the polar solvent, the neutral compound will preferentially partition into the nonpolar phase,whereas the polar constituent will preferentially partition into the polar phase. Separating the two phases effects a separation of the two solutes.

Carboxylic acids and phenols (1 and 3, Eqs. 5.10 and 5.11, respectively) aretwo classes of organic compounds containing functional groups that are polar

and hydrophilic (water-loving). Unless they contain fewer than about six carbonatoms, such compounds are generally either insoluble or only slightly soluble

in water because of the hydrophobic (water-avoiding) properties of the carbon-containing portion, R or Ar, of the molecule. They are soluble in common organicsolvents like dichloromethane or diethyl ether that have at least modest polarity(Table 3.1, p. 96). Consequently, carboxylic acids or phenols dissolved in diethylether, for example, will largely remain in that phase when the solution is extractedwith water.

R C

O

O

H

B–

Na+ (aq) R C

O–

O

BNa+

H++

1 2

A carboxylic acid

Water insoluble

Kwater/org < 1

A base

(as sodium salt)

A carboxylate

(as sodium salt)

Water soluble

Kwater/org > 1


(5.10)

Now consider what happens if the organic solution is extracted with a basic

aqueous solution. If the base, B–, is strong enough, the organic acid 1 or 3 will beconverted into the corresponding conjugate base 2 or 4 (Eqs. 5.10 and 5.11). Because it is a salt, the conjugate base is highly polar, and Kwater/org .1. Thus theconjugate bases of organic acids may be selectively extracted from an organic phaseinto an aqueous phase. If the basic extract is then neutralized by an acid such ashydrochloric acid, the conjugate base 2 or 4 will be protonated to regenerate theorganic acid 1 or 3 (Eqs. 5.12 and 5.13). Because the acid is water-insoluble, it willappear as either a precipitate or a second layer, if it is a liquid. The desired organicacid may then be recovered by filtration or separation of the layers.

Thus, two water-insoluble organic compounds, HA, which is acidic, and N, whichis neutral, that are dissolved in an organic solvent may be separated by selectivelyextracting the acidic compound into a basic aqueous phase. After the aqueous and organic phases are separated, HA is recovered from the aqueous phase uponneutralization, and N is obtained by removing the organic solvent (Fig. 5.1).

The choice of the base is determined by the acidity of the organic acid HA. Thisis defined in aqueous solution by Ka in Equation 5.14 and is often expressed as pKa(Eq. 5.15).

(5.14)

pKa 5 2log10 Ka (5.15)

The next step in determining what base is needed is to consider the equilibriumshown in Equation 5.16, in which HA is the organic acid, B– is the base being used,and HB is the conjugate acid of this base. The equilibrium constant, Keq, for thisprocess is given by Equation 5.17. Given the expressions for Ka for HA and HB

(Eqs. 5.14 and 5.18, respectively), Equation 5.17 transforms to Equation 5.19. From thisequation we see that log10 of the equilibrium constant, Keq, equals pKa(HB) – pKa(HA).We can predict how effective a particular base B– will be in converting an organic

Ka(HA) =[A-][H3O+]

[HA]

+ Na+ Cl–Ar O

H

HNa+

Cl+

4

Water soluble

3

Water insoluble

Ar O–

R C

O–

O

+ Na+ Cl–

R C

O

HNa+

Cl+

2 1

Water soluble Water insoluble

(aq)

H

O

Ar O

H

B– Na+ (aq) Ar O–

BNa+ H+

3

A phenol (Ar = aryl)

Water insoluble

Kwater/org < 1

A base

(as sodium salt)

4

A phenoxide

(as sodium salt)

Water soluble

Kwater/org > 1


(5.11)

(5.12)

(5.13)

acid HA to its anion simply by knowing the relative acidities of HA and HB. Theequilibrium for Equation 5.14 will lie to the right; namely, log10 Keq will be > 1 when-ever the acidity of HA is greater than that of HB.

(5.16)

(5.17)

(5.18)

(5.19)

Let’s now consider two specific examples of mixtures of acidic and neutralcompounds. Assume that you have a solution of benzoic acid (5) and naphthalene (7),a neutral compound, in diethyl ether and that you wish to separate the two. Bothcompounds and the solvent are insoluble in water at room temperature. The strategy is to convert 5 to its water-soluble conjugate base 6 by using an aqueousbase to extract the organic solution. The pKa of benzoic acid is 4.2, so any basewhose conjugate acid has a pKa greater than this will yield a value of log10 Keq > 1(Eq. 5.19). Aqueous hydroxide, whose conjugate acid is water (pKa 15.7), wouldgive log10 Keq 5 10.5, which means that this base will be extremely effective for theextraction of 5 into the aqueous phase. Indeed, aqueous hydroxide is commonlyused for extracting organic acids into an aqueous phase.

Keq =

Ka(HA)

Ka(HB) and log10 Keq = log10 Ka(HA) - log10 Ka(HB)

Ka(HB) =[B

–][H3O+]

[HB]

Keq =[A

–][HB]

[HA][B–]

HA + B-K

eq

∆ A-+ HB


5 6 7

C

O

O–C

O

OH

Benzoic acid Benzoate Naphthalene

Other aqueous bases could also be used. For example, carbonate (8) and bicar-bonate (9) would also work because their conjugate acids, 9 and 10 (Eq. 5.20), havepKas of 10.3 and 6.4, respectively. These bases are not as strong as hydroxide, so on thepurely thermodynamic basis described by Equation 5.19, they would provide a lowervalue of log10 Keq. However, both 8 and 9 may be converted to carbonic acid (10) upondi- and monoprotonation, respectively (Eq. 5.20). Carbonic acid is kinetically unstableand decomposes to carbon dioxide and water (Eq. 5.21), and this disrupts the equilib-rium of Equation 5.16, driving it to the right as HB, in the form of 10, undergoesdecomposition. The net result would be efficient deprotonation of 5 by these bases.

HA

N

Extract withaqueous base

Aqueous

phase

Organic

phase

Neutralize

with acid

Remove

solvent

A–

N

HA

N

Figure 5.1

Separating an acidic compoundand a neutral compound.

(5.20)

H2CO3 CO2 1 H2O (5.21)

C

O

8

O––OC

O

O–O

H3O+

9

HC

O

OOH

10

H

H3O+

Carbonate Bicarbonate Carbonic acid


11

OH

12

O–

2-Naphthol 2-Naphthoxide

It is important to recognize that the conversion of 10 into carbon dioxide andwater presents a practical problem when 8 and 9 are used to deprotonate acids forpurposes of extraction. If a separatory funnel is being used for the extraction, the gaspressure that results from the formation of carbon dioxide can blow out the stopcockand stopper, spraying the contents on you, your neighbors, or the floor. Alternatively,if a screw-cap vessel is being used, product may be ejected when the cap is loosenedto relieve the gas pressure. Accordingly, it is preferable to use hydroxide for basicextractions as a general rule.

Turning to a second example, assume you have a solution of 2-naphthol (11),which is a phenol, and naphthalene (7) in diethyl ether. The pKa of 11 is 9.5, so inthis case either aqueous hydroxide or carbonate would give Keq . 1; bicarbonate (8)is too weak a base to effect the deprotonation. Because aqueous hydroxide wouldprovide Keq .. 1, it is the base of choice for this extraction.

The examples discussed so far have involved separation of compounds havingdifferent acidities from neutral compounds. However, organic bases, usuallyamines, must sometimes be separated from mixtures containing organic acids andneutral compounds. Before considering how to perform such separations, it is useful to regard amines as being derivatives of ammonia where the hydrogenatoms on the nitrogen atom are replaced with substituted carbon atoms that aredesignated as R or Ar. Like the functional groups of carboxylic acids and phenols,the amino functional group is polar and hydrophilic, and amines having more thansix carbon atoms are either insoluble or only slightly soluble in water because ofthe hydrophobic properties of the R or Ar groups.

Amines are often soluble in aqueous acid at a pH , 4 because they are convertedinto their respective ammonium salts, the conjugate acids of the amines. This process isillustrated in Equation 5.22, wherein aqueous HCl serves as the acid. The enhancedionic character of the ammonium salt, as we saw before with the salts of carboxylicacids and phenols, makes it water soluble (Kwater/org . 1), whereas its parent base isnot (Kwater/org , 1). When the acidic solution is neutralized by adding aqueous base,the ammonium ion is deprotonated and converted into the original water-insolubleorganic base (Eq. 5.23) that will now either precipitate from solution or form a separatelayer. The amine may then be recovered by filtration or by separation of the layers.

(5.22)

ClR NH2 +

(Water insoluble)

Kwater/org < 1

(Water soluble)

Kwater/org > 1

H Cl (aq) RNH2 H .. –+

(5.23)

The question now is: How can the two water-insoluble organic compounds, B,

which is basic, and N, which is neutral, that are dissolved in an organic solvent beseparated? This problem is analogous to the earlier one of separating two water-insoluble organic compounds, HA, which is acidic, and N, which is neutral(see Fig. 5.1). Namely, the basic compound can be selectively extracted into anacidic aqueous phase as the soluble salt HB+. After the aqueous and organic phasesare separated, B is recovered from the aqueous phase upon neutralization, and N isobtained by removing the organic solvent (Fig. 5.2).

One example of an amine is 4-nitroaniline (13), which is converted into the cor-responding anilinium ion 14 by aqueous hydrochloric acid. Although 4-nitroanilineis a weak base with a pKb of 13.0, its conjugate acid 14 has a pKa of 1.0 and is a rela-tively strong organic acid. Hence, it is necessary to use a strong aqueous acid suchas 6 M HCl, in which the acid is actually the hydronium ion, H3O+, having a pKa ofabout –1.7, to convert 13 efficiently into its salt 14.

RNH2

(Water insoluble)

Kwater/org < 1

(Water soluble)

Kwater/org > 1

H Cl– + HO Na (aq) R NH2 + H2O + NaCl

..–+ +


Aqueous

phase

Organic

phase

Extract with

aqueous acid

B

N

HB+

N

Neutralize

with base

Remove

solventN

B

Figure 5.2

Separating a basic compound and a neutral compound.

NH2

NO2

13

NH3Cl

NO2

14

4-Nitroaniline 4-Nitroanilinium hydrochloride

+

In the experimental procedures that follow, three types of separations of neutral,acidic, and basic compounds are described. The first involves separating a mixture ofbenzoic acid (5) and naphthalene (7), using aqueous hydroxide for the extraction. Theflow chart for this separation corresponds to that of Figure 5.1. The second procedureinvolves separating a mixture of 5, 7, and 2-naphthol (11). In this case, 5 is first selec-

tively removed from the solution by extraction with aqueous bicarbonate, which does

not deprotonate 11. A second basic extraction using aqueous hydroxide removes 11

from the organic solution. The flow chart for this sequence is depicted in Figure 5.3.The last procedure involves separating a three-component mixture containing

benzoic acid (5), naphthalene (7), and 4-nitroaniline (13). First 13 is selectively

removed from the organic solution by extraction with aqueous hydrochloric acid,and then 5 is removed by extraction with aqueous base, leaving 7 in the organicsolution. The flow chart for this sequence of operations is shown in Figure 5.4. Allprocedures demonstrate the power of using the pH-dependence of water solubilityof organic compounds as a basis for separation. Such procedures for the prepara-tive separation of organic compounds are much easier than the chromatographicseparations you will learn about in Chapter 6.


5

7

11

Extract withbicarbonate

Aqueous

phase

Organic

phase

Neutralizewith acid

Extract withhydroxide

6

7

11

5

Organic

phase

Aqueous

phase

7

12

Removesolvent

Neutralizewith acid

7

11

Figure 5.3

Separating a neutral compoundand two compounds having differing acidities.

Aqueous

phase

Organic

phase

Extract with

hydroxide

5

7

6

7

Neutralize

with acid

Remove

solvent

5

7

Extract with

aqueous acid

14 13Aqueous

phase

Neutralization

with base

Organic

phase

5

7

13

Figure 5.4

Separating an acidic, a basic, anda neutral compound.

E X P E R I M E N T A L P R O C E D U R E S

Base and Acid Extractions

Purpose To separate multicomponent mixtures as a function of pH of solution.

S A F E T Y A L E R T

1. Do not allow any of the chemicals used in this experiment to come in con-

tact with your skin. If they do, immediately wash the affected areas with soap

and water.

2. Diethyl ether is extremely volatile and flammable. Be certain there are no

flames in your vicinity when using it for extraction and when removing it from

the “Neutral Compound.”

3. Wear latex gloves for the extractions, and use caution in handling wet glass-

ware, because it can easily slip out of your grasp.

4. When extracting a solution, vent the separatory funnel or vial often to avoid

a buildup of pressure.

M I N I S C A L E P R O C E D U R E

Preparation Sign in at www.cengage.com/login to answer Pre-Lab Exercises,

access videos, and read the MSDSs for the chemicals used or produced in this

procedure. Read or review Sections 2.7, 2.10, 2.11, 2.13, 2.17, 2.21, 2.24, 2.25,

2.29, 3.2, and 3.3.

w


A. One-Base Extraction

Apparatus Separatory funnel, ice-water bath, apparatus for vacuum filtration, sim-

ple distillation, and flameless heating.

Dissolution Obtain 2 g of a mixture of benzoic acid and naphthalene. Dissolve the

mixture by swirling it with 30 mL of diethyl ether in an Erlenmeyer flask. If any solids

remain, add more diethyl ether to effect complete dissolution. Transfer the solution

to the separatory funnel.

Extraction Extract the solution with a 15-mL portion of 2.5 M (10%) aqueous

sodium hydroxide. Be sure to hold both the stopcock and the stopper of the funnel

tightly and frequently vent the funnel by opening its stopcock (Fig. 2.61). Identify

the aqueous layer by the method described in Section 2.21, transfer it to an Erlen-

meyer flask labeled “Hydroxide Extract,” and transfer the organic solution into a

clean Erlenmeyer flask containing two spatula-tips full of anhydrous sodium sul-

fate and labeled “Neutral Compound.” Let this solution stand for about 15 min,

occasionally swirling it to hasten the drying process. If the solution remains cloudy,

add additional portions of sodium sulfate to complete the drying process.w

Precipitating and Drying Cool the “Hydroxide Extract” in an ice-water bath.

Carefully acidify this solution with 3 M hydrochloric acid, so that the solution is

distinctly acidic to pHydrion™ paper.w Upon acidification, a precipitate should

form; cool the mixture for 10–15 min to complete the crystallization.

Collect the precipitate by vacuum filtration (Fig. 2.54) using a Büchner or

Hirsch funnel. Wash the solid on the filter paper with a small portion of cold water.

Transfer the solid to a labeled watchglass, cover it with a piece of filter or

weighing paper, and allow the product to air-dry until the next laboratory period.

Alternatively, dry the solid in an oven having a temperature of 90–100 °C for about

1 h. After drying, transfer the benzoic acid to a dry, tared vial.

Separate the “Neutral Compound” from the drying agent by decantation

(Fig. 2.56) or gravity filtration through a cotton plug (Fig. 5.5) into a 100-mL round-

bottom flask. Remove the solvent by simple distillation (Fig. 2.37). Alternatively, use

rotary evaporation or one of the other techniques described in Section 2.29. Allow

the residue to cool to room temperature to solidify, scrape the contents of the flask

onto a piece of weighing paper to air-dry, and then transfer it to a dry, tared vial.

Analysis and Recrystallization Determine the weight and melting point of each crude

product. If you know the relative amounts of benzoic acid (5) and naphthalene (7) in

the original mixture, calculate the percent recovery of each compound. Recrystallize

them according to the general procedures provided in Section 3.2 and determine

the melting points of the purified materials.

B. Two-Base Extraction

Apparatus Separatory funnel, ice-water bath, apparatus for vacuum filtration,

simple distillation, and flameless heating.

Dissolution Obtain 2 g of a mixture of benzoic acid, 2-naphthol, and naphthalene.

Dissolve the mixture by swirling it with 30 mL of diethyl ether in a 125-mL Erlenmeyer

flask. If any solids remain, add more diethyl ether to effect complete dissolution.

Cotton plug

Cork ring

Ring support

Figure 5.5

Miniscale gravity filtrationthrough a cotton plug.

Extraction Extract the solution with a 20-mL portion of 1.25 M (10%) aqueous

sodium bicarbonate (Fig. 2.61). Caution: Gaseous carbon dioxide is generated!

To prevent accidental loss of material, do the following: After adding the aqueous

bicarbonate to the funnel, swirl the unstoppered funnel until all foaming has

subsided. Then stopper the funnel and, holding both the stopcock and the stopper

of the separatory funnel tightly, invert the funnel and immediately vent it by

opening the stopcock. Finally, shake the funnel with frequent venting until gas

is no longer evolved. Separate the layers, transferring the aqueous layer to a

125-mL Erlenmeyer flask labeled “Bicarbonate Extract.”w To ensure properly

identifying the aqueous layer, consult Section 2.21. Return the organic solution

to the separatory funnel.

Now extract the organic solution with a 20-mL portion of cold 2.5 M (10%)

aqueous sodium hydroxide, venting the funnel frequently during the process.

Transfer the aqueous layer to a 125-mL Erlenmeyer flask labeled “Hydroxide

Extract.” Transfer the organic solution to a 50-mL Erlenmeyer flask labeled

“Neutral Compound” and containing two spatula-tips full of anhydrous sodium

sulfate. Loosely cork the flask containing the organic solution, and let it stand

for at least 15 min with occasional swirling to promote drying. If the solution

remains cloudy, add additional portions of sodium sulfate to complete the

drying process.w

Precipitating and Drying For the “Bicarbonate” and “Hydroxide Extracts,” follow the

directions given in Part A for the “Hydroxide Extract.” Also apply the protocol

provided in Part A for the “Neutral Compound” to the corresponding solution

obtained in this procedure.


product. If you know the relative amounts of benzoic acid (5), naphthalene (7), and

2-naphthol (11) in the original mixture, calculate the percent recovery of each

compound. Recrystallize them according to the general procedures provided in

Section 3.2 and determine the melting points of the purified materials.

C. Acid-Base Extraction

Apparatus Separatory funnel, ice-water bath, apparatus for vacuum filtration, simple

distillation, and flameless heating.

Dissolution Obtain 1.5 g of a mixture of benzoic acid, 4-nitroaniline, and naphtha-

lene. Dissolve the mixture by swirling it with about 40 mL of dichloromethane in an

Erlenmeyer flask. Transfer the solution to the separatory funnel.

Extraction Extract the organic solution three times using 15-mL portions of 3 M

hydrochloric acid. Be sure to hold both the stopcock and the stopper of the

funnel tightly and frequently vent the funnel by opening its stopcock (Fig. 2.61).

Identify the aqueous layer by the method described in Section 2.21. Combine the

three acidic aqueous layers from the extractions in an Erlenmeyer flask labeled

“HCl Extract.” Return the organic layer to the separatory funnel and extract it two

times using 15-mL portions of 3 M sodium hydroxide solution. Combine these two

aqueous layers in a second flask labeled “Hydroxide Extract.” Transfer the

organic solution into a clean Erlenmeyer flask containing two spatula-tips full of

anhydrous sodium sulfate and labeled “Neutral Compound.” Let this solution


stand for about 15 min, occasionally swirling it to hasten the drying process. If

the solution remains cloudy, add additional portions of sodium sulfate to complete

the drying process.w

Precipitating and Drying Cool the “HCl Extract” and the “Hydroxide Extract” in an

ice-water bath. Neutralize the “HCl Extract” with 6 M sodium hydroxide and add a

little excess base to make the solution distinctly basic to pHydrion paper. Neutralize

the “Hydroxide Extract” with 6 M hydrochloric acid and add a little excess acid to

make the solution distinctly acidic to pHydrion paper.w Upon neutralization, a

precipitate should form in each flask.

Collect the precipitate in the flasks labeled “HCl Extract” and “Hydroxide

Extract” by vacuum filtration (Fig. 2.54) using a Büchner or Hirsch funnel. Wash

each solid on the filter paper with a small portion of cold water. Transfer each solid

to a labeled watchglass, cover it with a piece of filter or weighing paper, and allow

the product to air-dry until the next laboratory period. Alternatively, dry the solid in

an oven having a temperature of 90–100 °C for about 1 h. After drying, transfer

the 4-nitroaniline and the benzoic acid each to a different dry, tared vial.

Separate the “Neutral Compound” from the drying agent by decantation

(Fig. 2.56) or gravity filtration through a cotton plug (Fig. 5.5) into a 100-mL round-

bottom flask. Remove the solvent by simple distillation (Fig. 2.37). Alternatively,

use rotary evaporation or one of the other techniques described in Section 2.29.

Allow the residue to cool to room temperature to solidify, scrape the contents of

the flask onto a piece of weighing paper to air-dry, and then transfer it to a dry,

tared vial.


product. If you know the relative amounts of benzoic acid (5), naphthalene (7), and

4-nitroaniline (13) in the original mixture, calculate the percent recovery of each

compound. Recrystallize them according to the general procedures provided in

Section 3.2 and determine the melting points of the purified materials.

M I C R O S C A L E P R O C E D U R E

Preparation Sign in at www.cengage.com/login to answer Pre-Lab Exercises,

access videos, and read the MSDSs for the chemicals used or produced in this

procedure. Sections 2.7, 2.9, 2.10, 2.17, 2.21, 2.25, 2.29, 3.2, and 3.3.

A. One-Base Extraction

Apparatus A 5-mL conical vial, Pasteur filter-tip pipets, ice-water bath, 3-mL Craig

tube, apparatus for Craig tube filtration and flameless heating.

Dissolution Obtain 0.2 g of a mixture of benzoic acid and naphthalene. Dissolve the

mixture by swirling it with 2 mL of diethyl ether in the conical vial. If any solids remain,

use a filter-tip pipet to add enough diethyl ether to effect complete dissolution.

Extraction Add 0.5 mL of cold 2.5 M (10%) aqueous sodium hydroxide to the vial

and cap it. Shake the vial vigorously for a minute or two, occasionally unscrew-

ing the cap slowly to relieve any pressure. Allow the layers to separate and, using

a Pasteur pipet, transfer the aqueous layer to a Craig tube labeled “Hydroxide

Extract.” To ensure properly identifying the aqueous layer, consult Section 2.21.


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Experimental organic chemistry (Extraction)

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Transcript of Experimental organic chemistry (Extraction)