Are you really ready?

Lets get set for

a Separation
Chemistry
lecture!
Solvent Extraction

X Extraction: transfer of a solute from

one phase to another.
X Can use most any combination of
phases (solid, liquid, gas, supercritical
fluid)
X Solvent extractions use two immiscible
liquids.
hTypically aqueous/organic solvent combos
Solvent Extraction

X Organic solvents less dense than water

hdiethyl ether, toluene, hexane
X Organic solvents more dense than water
h chloroform, CCl4, dichloromethane
X Like dissolves like so ideally, the
extracting solvent should be similar to
the solute (analyte)
Properties of Extraction Solvents

XSolvents used for extraction

1. immiscible with water (polarity)
2. high solubility for organic compound
3. relatively low boiling point (removal)
4. non-toxic, cheap, available

Xmethylene chloride, diethyl ether, hexane, ethyl acetate

Xdensities determine top or bottom
Extraction done by our mothers

XSolid-Liquid Extraction
hbrewing tea
hpercolating coffee
hspices and herbs
Solvent Extraction

Separatory
funnel

add second
immiscible
solvent

shake
Solvent Extraction

X Solute partitions between the two

phases

Phase 2 [S]2

Phase 1 [S]1
Theory of Liquid-Liquid Extraction

XDifferential solubility in two immiscible solvents

organic product
Immiscible solvents
impurity
Theory of Extraction

XIf KD ~ 1, dont get good separation.

Little separation: low yield

Extraction Theory

XSeparation depends upon relative

solubility of the compound in each of the
two immiscible solvents.
g / mL(organic )
KD =
g / mL(water )
(g/mL is solubility)
want KD >>>> 1 or <<<<<<1
Solvent Extraction

XEquilibrium constant for this

partitioning is K (partition coefficient)

[S]2
K=
[S]1
Solvent Extraction

X Determination of solute concentration

in each phase
X Define some variables:
h V1 & V2 are volumes of solvents 1&2
h m = total # of moles of solute (S) present
h q = fraction of solute remaining in phase 1
at equilibrium
Solvent Extraction

X[S]1 = qm/V1
X[S]2 = (1-q)m/V2
Solvent Extraction

[S]2 (1-q)m/V2 (1-q) /V2

K= = =
[S]1 qm/V1 q/V1
Rearrange:

V1 KV2
q= (1-q) =
KV2 + V1 KV2 + V1

fraction of S in: phase 1 phase 2

Solvent Extraction

X If remove V2 and extract V1 with fresh

layer of V2, what fraction remains in V1?
h Initial moles = m
hafter first extraction - qm
hafter second extraction - q(qm)=q2m

V1 2
q(2) =
KV2 + V1
Solvent Extraction

X Fraction in V1 after n extractions:

V1 n
q(n) =
KV2 + V1
Solvent Extraction

X Example: Solute A has a partition

coefficient of 4.000 between hexane and
water. (K = [S]hexane/[S]water = 4) If
150.0 ml of 0.03000 M aqueous A is
extracted with hexane, what fraction of
A remains if:
Solvent Extraction

Xa) one 600.0 ml aliquot of hexane is

used?
150ml
q= = 0.05882 = 5.882%
4(600ml) + 150ml

# moles remaining
0.05882 (0.03M0.150L) = 2.647x10-4 moles
Solvent Extraction

Xb) 6 successive 100.0 ml aliquots of

hexane are used?

150ml 6
q= = 0.0004115
4(100ml) + 150ml

# moles remaining
4.115 x 10-4 (0.03M0.150L) = 1.852x10-6moles
Solvent Extraction

X Although same volume of hexane is

used, it is more efficient to do several
small extractions than one big one!
h1 600 ml extraction extracts 94.12%
h6 100 ml extractions extract 99.96%
Solvent Extraction (pH effects)

X with organic acids/bases:

Ka
HA H+ + A-
Kb
B + H2O BH+ + OH-
Generally, neutral species are more soluble
in an organic solvent and charged species
are more soluble in aqueous solution
Solvent Extraction (pH effects)

X Partitioning of organic acids between

two phases:
very little here, ions
have poor solubility
organic HA H+ + A-

Ka
aqueous HA H+ + A-
Solvent Extraction (pH effects)

X When the solute (acid/base) can exist in

different forms, D (distribution
coefficient) is used instead of K
(partition coefficient)
Solvent Extraction (pH effects)

total conc. in phase 2

D=
total conc. in phase 1
HA [HA]org
D=
K [HA]aq + [A-]aq
Ka
HA H+ + A-
Solvent Extraction (pH effects)

X Substitute for [A-] in D eq. and

rearrange
[H+][A-] Ka [HA]
Ka = [A-] =
[HA] [H+]
[HA]2
D=
Ka [ HA]1
[HA]1 + +
[H ]
Solvent Extraction (pH effects)

[HA]2 [HA]2
D= =
Ka [ HA]1 K
[HA]1 + + [HA] 1 + a
+
[H ] 1
[ H ]

Ka [HA]2
D 1+ + = =K
[ H ] [HA]1
Solvent Extraction (pH effects)

Ka
D 1+ + = K
[ H ]

+
K K[ H ]
D= = +
Ka [ H ] + K a
1+ +
[ H ]
Solvent Extraction (pH effects)

X pH effect on D for organic acids

[H+]=Ka
[H+]>>Ka
pH=pKa
K

mainly mainly
D HA A-

[H+]<<Ka

pH
Solvent Extraction (pH effects)

X Example problem: Want to separate two

organic acids using a scheme based on pH.
Acid 1 (pKa = 4), Acid 2 (pKa = 8)
K1 Acid 2 stays in
K2 organic phase,
acid 1 is extracted
D into aqueous phase

4 pH 8
Solvent Extraction (pH effects)

X Analogous treatment for organic bases

(proton acceptors, not KOH)
[H+]=Ka
pH=pKa [H+]<<Ka
K
K Ka
D= mainly mainly
[H+] + Ka D BH+ B
[H+]>>Ka

pH
Solvent Extraction (pH effects)

X In general:
acid base
K

pH
Separate organic acid, base
and neutral analytes

Initial Aq. phase

pH=1, extract with ether

Aq. Phase Ether Phase
Org. base Org. acid, Org. neutral

extract with pH=12 Aq. Soln

Aq. Phase Ether Phase

Org. acid Org. neutral
 Calculations

XDetermine KD for extraction of solid

in the two solvents
unk ( g ) / solvent (mL)
KD =
unk ( g ) / water (mL)
Practice Calculations

Mass solid 120 mg

Total volume organic solvent 1.5 mL
Total volume water 1.5 mL
Mass solid extracted into 92 mg
organic solvent
Mass remaining in water 120-92 = 28 mg
KD = 92 mg/1.5 mL = 3.3
28 mg/1.5 mL
Yes, I am full, confused

XTake a little break?

XYo, wis semene dhisik..