lecture 2 Extraction

" Separation of Acidic Substances Notes"

Introduction

Acids and Bases are one the most fundamental principles of chemistry. Acidity
and basicity are involved in determining chemical reactivity, separation,
solubility, and transport of molecules across membranes.

Background:

Aqueous (water based) solvents are very polar. Organic solvents are much
less polar than aqueous solvents. The underlying principle behind acid
extractions begins with the fact that many neutral organic compounds are not
soluble in water but are soluble in organic solvents.

If a neutral organic compound is converted to an ion by reaction with a base,

then the polarity of that compound is significantly increased. The ion typically
has a high solubility in water and a reduced solubility in the organic solvent.
This often causes the ion to migrate to the aqueous phase from the organic
phase.

Explain the experiment

One possible experiment begins with two neutral organic compounds

(benzoic acid and 2-naphthol) dissolved in an organic solvent, MTBE (methyl
t-butyl ether). A base is added which will selectively react with one of the
materials and convert it into its conjugate base (an ion). This ion has a high
solubility in water and a low solubility in MTBE, so it will migrate (partition)
to the aqueous phase. The aqueous phase is removed along with the conjugate
base of the first compound. This layer is later acidified, protonating the
conjugate base. The solubility of the neutral material in water is low, and the
compound precipitates and is recovered by filtration. This process is repeated
with the addition of a stronger base to the MTBE which will react with the
second compound and that material will deprotonate, form an ion then
partition to the aqueous phase. Again the aqueous layer is removed, acidified
and the precipitated neutral material is recovered.

material for this experiment:

1. Concentrated Hydrochloric Acid is a strong acid

2. Sodium Hydroxide Solution (1.5M) is corrosive even though it is not
very concentrated.
3. Separatory Funnels
4. Methyl t-Butyl Ether (MTBE) is an organic solvent with a moderately
high vapor pressure.

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The Bronsted-Lowry Theory of acids and bases:

An acid is a proton (hydrogen ion) donor (lose a proton )and form a conjugate
base. HA -> H+ + A-

The stronger the acid, the weaker the conjugate base.

A base is a proton (hydrogen ion) acceptor and form a conjugate acid.

B- + H+ -> HB.

The stronger the base, the weaker the conjugate acid.

1. Some terminology related to Acid-base extractions:

Partitioni: The distribution of a substance or ions between two immiscible

liquids.
Extractionii: Dissolution and removal of one constituent of a mixture in a
solvent.
Precipitation: If the concentration of a compound in a solvent is greater than
the solubility of that compound, the compound will no longer remain
dissolved and will form a new solid phase.

Equilibruium Constant (K): The numberical value of the concentration of the

products divided by the concentration of the reactants.

 If the value of K is smaller than one, the equilibrium lies in favor of the
starting material. The reaction does not proceed greatly in the forward
direction.
 If the value of K is greater than one, the equilibrium lies in favor of the
products. The reaction proceeds in the forward direction.

pKa: The negative log of the acid equilibrium constant. pKa= - log Ka where
the acid equilibrium constanat Ka is equal to:

The smaller the pKa the stronger the acid.

2. Useful pKa information. (Do not memorize pKa values)

HA -> H+ + A-

ACID (HA) pKa CONJUGATE BASE (A-)

Hydrochloric Acid (HCl) pKa= -7.0 Chloride ion (Cl-)

Benzoic acid (Ph-CO2H) pKa = 4.17 Benzoate ion (Ph-CO2-)
Carbonic acid (H2CO3) pKa = 6.35 Bicarbonate ion(HCO3-)
2-Naphthol pKa = 9.5 2-Naphthonate ion
Water (H2O) pKa = 15.7 Hydroxide ion (HO-)

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3. Predicting if a reaction will proceed in the forward direction or
not
To determine if any acid-base reaction will succeed, as shown,
HA1 + -A2 → -A1 + HA2

First, identify the acid and the base on both sides of the arrow. Compare the
pKa of the acids. Determine if the stronger acid is on the right or the left of the
arrow. If the pKa of the acid on the left, HA1 is a smaller number (that is, the
acid is stronger) than the pKa of the acid on the right, HA2 then the reaction
will proceed in the forward direction. If the pKa of the acid on the left, HA1 is
larger (that is, the acid is weaker) than the pKa of the acid on the right, HA2,
then the reaction will not proceed in the forward direction (but it will proceed
in the reverse direction).

S.A. + S.B. W. B. + W. A.

W. B. + W. A. S.A. + S.B

4. Below are ALL the possible reactions for the lab.

Examine each reaction, assign acid and base to each compound, determine if
the reaction will proceed in the forward direction or not. Place an X across
each arrow which will not proceed in the forward direction. Only write the
reactions that WILL proceed in your lab notebook

1:

2:

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3:

5. Aqueous solutions are very polar. Organic solvents are less polar than
aqueous. Ions are very polar.

Typically ions have a higher solubility in water than organic solvents. Most
neutral organic compounds have limited solubility in water but an increased
solubility in organic solvents.

If a neutral organic compound dissolved in an organic solvent is deprotonated

and turned into an ion, the solubility in the organic solvent will be decreased
and the ion will want to move or partition into an available aqueous solvent.

IF a base is chosen which will selectively deprotante one of a mixture of

dissolved organic compounds and turn only into an ion, then mixtures of
compounds can be separated. This concept is why this separation experiment
is possible.

6. The two compounds are separated as ions dissolved in water. It is desired to

reform and isolate benzoic acid and 2-naphthol as pure solids. In order to do
this, a very strong acid is added to the aqueous solutions, this will reprotonate
the ions and turn them back into neutral organic molecules. Most neutral
organic compounds have a low solubility in water. 2-Naphthol and benzoic
acid are not an exception. As neutral compounds they have a low solubility in
the water, and hence will precipitate as a solid. The solid is isolated by vacuum
filtration. A melting point will be taken to assess the purity of these materials.

7. Separatory funnels are specially designed glassware for the separation of

immiscible liquids. They have a ground glass access port at the top and a
stopcock at the bottom. This is the most expensive piece of glassware in your
drawers. A new sep funnel costs approximately $110.00. Handle with care.

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  Place separatory funnel in ring clamp.
 Always place a receiver under stopcock
 picking up, shaking, venting, and draining your sep funnel
 attention One reaction produces CO2 gas which created more vapor
pressure.
 Waste MTBE must be disposed of in the non-halogenated organic
liquid waste container.
 Aqueous neutralized waste in which all of the organics have been
removed, may be disposed of down the drain.
 Given pKa, determine if a proposed reaction will proceed in the forward
direction or not.

Changes to the procedure can make the separation either more or less
efficient.
More extractions with smaller volumes are more efficient than one extraction
with the combined volume (Three 10 mL extractions are more efficient than
one 30 mL).

If a mixture of dissolved organic compounds is mixed with a strong base to

deprotonate both of them, they will both turn into ions, both migrate to the
aqueous phase and no separation will occur.

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 Flow sheet of Extraction Experiment

benzoic acid 2- naphthol

each material dissolve in MTBE in sep funnel

add 10 ml of saturated NaHCO3 solution.

shake, vent, separate, drain, *repeat.

flask A Compound remaining in

organic leyar.
what is in flask A?
what is thise compound?

flask B flask C
what is in flask B? what is in flask C?

SOLID IN
FLASK B