CHEM 233: Organic

Laboratory I Prelab Lecture

University of Illinois
at Chicago

UIC
O

H2O

protonation
+

R NH2

R NH3

H OH2

H2O

Na

OH

OH

H
N

amine
(conjugate base)

ammonium cation
(conjugate acid)

crude solid:
not pure/clean
depressed mp
possibly discolored

CH2Cl2

Lab 6: Base Extraction of Benzoic Acid from Acetanilide

followed by Recrystallization and mp Determination.
H
N

CH3
O

pure solid:
white crystals
sharp mp
narrow mp range

O
OH

(pKa = 4.20)

Keq
+

OH

H2O
(pKa = 15.7)

Todays Goals
O
O

H
N

CH3
O

benzoic acid
(m.p. = 121-123 C)

acetanilide
(m.p. = 111-115 C)

1. Separate ~1.0 g of a 1:1 w/w mixture of benzoic acid and acetanilide by baseextraction.
2. Purify each isolated solid by recrystallization from boiling water.
3. Measure melting points and compare to reported values.
4. Determine % yield obtained for each solid based on mass of starting mixture.
University of
Illinois at Chicago

UIC

2009, Dr. Chad L. Landrie

CHEM 233: Organic Chemistry Laboratory 1

Slide 2
Prelab Lecture: Lab 6

General Scheme for:

Base Extraction of 1:1 Benzoic Acid/Acetanilide
1. Neutralize/
Protonate
with 3 M HCl

H2O O
O

Na

2. Vacuum filter
precipitated
benzoic acid

O
OH
crude solid:
not pure/clean
depressed mp
possibly discolored

1. recrystallize
from boiling
water
2. vacuum filter

O
OH
pure solid:
white crystals
sharp mp
narrow mp range

H2O
O
O
O
OH

Add 3 M
NaOH (aq)

Na

OH

separate
layers

H
N

H
N

CH2Cl2

CH2Cl2 is denser
than water =
bottom layer

CH2Cl2

evaporate
CH2Cl2
CH2Cl2
H
N

H
N

CH3
O

crude solid:
not pure/clean
depressed mp
possibly discolored

University of
Illinois at Chicago

UIC

2009, Dr. Chad L. Landrie

CHEM 233: Organic Chemistry Laboratory 1

1. recrystallize
from boiling
water
2. vacuum filter

H
N

CH3
O

pure solid:
white crystals
sharp mp
narrow mp range

Slide 3
Prelab Lecture: Lab 6

Three Readily Ionizable Functional Groups That

are Separable by Acid or Base Extractions
O
R

deprotonation
O

OH

carboxylic acid
(conjugate acid)

O
R

H2O

H2O

H2O

carboxylate anion
(conjugate base)

deprotonation
OH

phenol
(conjugate acid)

phenoxide anion
(conjugate base)

protonation
+

R NH2
amine
(conjugate base)

H OH2

R NH3
ammonium cation
(conjugate acid)

*Hydroxide and hydronium were chosen as general examples; other specific acids and bases may be used.
The counterion on the left of the equilibria will depend upon the specific acid or base on the left.
University of
Illinois at Chicago

UIC

2009, Dr. Chad L. Landrie

CHEM 233: Organic Chemistry Laboratory 1

Slide 4
Prelab Lecture: Lab 6

Solubility--Like Dissolves Like

O

O
R NH3

Water Polarity

water soluble
ionic and very polar
small organic ion

O
H

O
R NH2

H
R

water insoluble; organic solvent soluble

nonionic, but polar functional groups
i.e. organic solvent = CH2Cl2
University of
Illinois at Chicago

UIC

VSEPR = water is bent; bond

angles of 104.5
strong molecular dipole
inorganic and very polar (=80)
well suited to dissolve ionic
compounds, including small
organic anions and cations

2009, Dr. Chad L. Landrie

CHEM 233: Organic Chemistry Laboratory 1

Slide 5
Prelab Lecture: Lab 6

Choosing an Effective Extracting Acid or Base

For an Effective Acid or Base Extraction, Keq must be > 1.0
pKeq = pKa (acid left) - pKa (acid right)
Keq = 10

remember: p = -log10
For derivation of this
equation, see text page 154.

-[pKa (acid left) - pKa (acid right)]

Base Extraction
HA

organic
acid (left)

extracting
base

Keq

Acid Extraction
Keq

BH

HA

extracting
conjugate
acid (right)

organic
conjugate
base

organic
base

extracting
acid (left)

Example:

HB

extracting
conjugate
base

organic
conjugate
acid (right)

Example:

O
OH

Keq
+

OH

N H
H
+

(pKa = 4.20)

H2O
(pKa = 15.7)

Keq
HCl

H3CO

H
N H
H

Cl

H3CO
(pKa = -8.0)

(pKa = 5.20)

pKeq = 4.20 - 15.7

Keq = 10 -(-11.5) = 3.16 x 1011

pKeq = -8.0 - 5.20

Keq = 10 -(-13.2) = 1.58 x 1013

Since Keq is large (>>1), aqueous hydroxide is a

good extracting solvent for benzoic acid.

Since Keq is large (>>1), aqueous HCl is a good

extracting solvent for 4-methoxyaniline.

University of
Illinois at Chicago

UIC

2009, Dr. Chad L. Landrie

CHEM 233: Organic Chemistry Laboratory 1

Slide 6
Prelab Lecture: Lab 6

Several Smaller Extractions are More Effective

than One Large Extraction with Same Volume

FA =

Vo
KVx + Vo

FA = fraction of solute remaining in original solvent

K = partition coefficient = ([Ax]/[Ao])
larger K = more efficient extracting solvent
Vo = volume of original solvent
Vx = volume of extracting solvent (per extraction)
n = number of extractions

Example one: 3 extractions x 5 mL each

(15 mL total) from 20 mL of Vo. K = 2.

20
FA =
2*5 + 20
FA = 0.30

**30% of solute remains in the original solvent.**

University of
Illinois at Chicago

UIC

Example two: 1 extractions x 15 mL

each (15 mL total) from 20 mL of Vo. K = 2.

20
FA =
2*15 + 20
FA = 0.40

**40% of solute remains in the original solvent.**

2009, Dr. Chad L. Landrie

CHEM 233: Organic Chemistry Laboratory 1

Slide 7
Prelab Lecture: Lab 6

General Requirements for Extracting Solvent

1. Does not react irreversibly with the solute.
2. Immiscible with original solvent.
(i.e. H2O and CH2Cl2)
3. Selectively removes desired component.
(i.e. large K for component to be extracted and small K for the rest.)
4. Easly separated from the solute.
(i.e. cyrstallizatio/precipitation then filtration,distillation)

University of
Illinois at Chicago

UIC

2009, Dr. Chad L. Landrie

CHEM 233: Organic Chemistry Laboratory 1

Slide 8
Prelab Lecture: Lab 6

Recrystallization
Dissolve product and
impurities in a minimum
amount of solvent at high
temperature.

Cool solution. Product

crystallizes out of
solution. Impurities
remain dissolved.

Desired Product
(yellow/large circles)
+
Impurities
(small/blue circles)

Requirements for Recrystallization Solvent

1. Not reactive with desired product(s).

Vacuum filter solution

through a Buchner funnel.
Mother liquor (filtrate)
contains impurities.

2. Desired product is completely soluble at elevated

temperature, but only slightly solubleor not soluble at
allat room temperature.
3. Undesired components (impurities) are highly soluble
at all temperatures (small temperature coefficient).
4. Easily removed from crystalline product by filtration
and evaporation.
University of
Illinois at Chicago

UIC

2009, Dr. Chad L. Landrie

CHEM 233: Organic Chemistry Laboratory 1

filtrate

Slide 9
Prelab Lecture: Lab 6