Extraction

Multiple Batch Extraction

Multiple Batch Extraction
Sometimes the quantitative extraction of a solute is not accomplished
in a single step.

Your options typically are to:

Increase the volume of the extracting solvent - not usually a good

idea.

Use multiple extractions.

Multiple Batch Extraction
For multiple extractions, it is useful to compute
the fraction of analyte remaining unextracted
after a given number of extractions

Remember that the percent extraction,

100D
%E =
D + (V2/V1)

If we divide this equation by 100,

D
%E =
D + V2/V1
Multiple Batch Extraction
Substraction of this from 1 gives F, the
fraction remaining unextracted:

D
F=1-
D + (V2/V1)

Which can be rearranged to,

V2
F =
DV1 + V2
Multiple Batch Extraction
V1 and V2 can be any two immiscible phases, but
commonly organic and aqueous;
We have used V2 to represent the volume containing the
initial solute.
If W0 (the initial quantity [grams or moles] or
concentration of analyte in the initial (aqueous) phase)
is multiplied by the previous equation,
then the quantity or concentration remaining in the phase
after one extraction, W2 is
V2
W2 = W0
DV1 + V2
Multiple Batch Extraction
• If n separate extractions are performed with
equal volumes of V1 then W2 should be
multiplied by F a total of n times:

n
V2
W2 = W0
DV1 + V2
Multiple batch extractions
Example:
One gram of a solute is contained in 100 ml of an aqueous
solution. Calculate the amount remaining in the aqueous
phase after (a) a single extraction with 90 ml of an organic
solvent with appropriate reagents, (b) a single extraction
with 30 ml extraction; and (c) three successive extractions
with 30 ml solvent, assuming that the distribution ratio
for the extraction is 10.
Multiple batch extractions
(a) 100 = 0.100 g
W2 = 1.00
10 x 90 + 100

(b) 100 = 0.250 g

W2 = 1.00
10 x 30 + 100

3
(c) 100 = 0.0156 g
W2 = 1.00
10 x 30 + 100

Thus, 90% of the solute is extracted with 90 ml solvent, 75%

is extracted with 30 ml solvent, but 98.4% is extracted by
three 30-ml portions of the solvent
Countercurrent extractions
A precursor to chromatography
When two solutes to be separated have D of the same order of magnitude,
their separation efficiency in a single-batch extractions is very poor.
(Even if the D values for two solutes differ by 1000, you still can’t get better
than 97% purity.)

What do we do if the goal is to separate two species with similar D values?

Countercurrent extractions
• A technique of successive extractions with
fresh solvent, complex mixtures with similar
distribution may be separated.

We add the
extracting phase
to the next tube
and add fresh
phase to the first

n= 0 1 2 3
Countercurrent extractions
Assume
Equimolar amounts of solutes A and B.
Equal volumes of both phases
A single extraction with an organic phase removes
3% of A and 97% of B.
After each extraction, you transfer the organic
phase to the next tube and add fresh organic to
the original one.
Countercurrent
Totals
extractions
A 100
B 100

We add 100 B
fresh 100 A
organic
solvent
into tube
#0 & mix 0 1 2 3
n=
Countercurrent
Totals
extractions
We move the
organic layer into
A 100 the next tube
containing fresh
B 100 aqueous solvent

97 B
3A

3B
97 A

After mixing
n= 0 1 2 3
Countercurrent
Totals
extractions
A 97 3
B 3 97

97 B
3A
We add
fresh
3B
organic
97 A
solvent
into tube
#0 & mix

n= 0 1 2 3
Countercurrent
Totals
extractions
A 97 3
B 3 97

97 B
3A

3B
97 A

n= 0 1 2 3
Countercurrent extractions
Next, the organic phase is
transferred to the second tube

A new equilibrium is established

The process is continued

Countercurrent
Totals
extractions
A 97 3
B 3 97

2.91 B 94.09 B
2.91 A 0.09 A

0.09 B 2.91 B
94.09 A 2.91 A

n= 0 1 2 3
Countercurrent extractions
Materials with larger D values tend to move
along with the organic (mobile) phase more
rapidly
Countercurrent extractions
As the number of tubes are increased, the distribution
of solutes appears more Gaussian. Ultimately, you
can resolve them

Note that the peaks broaden and shorter as the

number of tubes increases. As the number of transfer
increases (number of tubes increases), the solute
spread through a larger number of tubes.
Continuous extraction
• In some cases, it is difficult to efficiently remove a solute unless a
large number of extractions are conducted.

• An alternate approach is a continuous extraction.

• With an appropriate setup, an efficient extraction can be conducted

with a minimum of extracting solvent.
Continuous extractions
Advantages
• Only uses a small amount of solvent
• Can remove a high percent of a solute
• Can work unattended for long periods

Setup
Dependent on relative density of liquids or if solids are to be
extracted.
Continuous extraction
• Setup when the
extracting fluid is
more dense
Continuous extraction
• Setup when the
extracting fluid is
less dense
Continuous extraction
For these systems to work
• density difference must be high
• solute being collected must be less volatile than the extracting solvent
• solute being collected must be thermally stable under conditions
used
Continuous extraction
• Continuous
extraction can also
be applied to
solids.
• Major limitation is
a loss in efficiency
during extraction
due to channels
developing in the
solid
Soxhlet extraction
• An alternate approach
of extracting solids.
• Repeated soaking of
the solid prevents
formation of channels
• Rapid return of cool
liquid can represent a
hazard. Solvent should
not be flammable

QuickTime™ and a
Graphic s decompressor
are needed to see this picture.
Soxhlet extraction
A schematic representation of a
Soxhlet extractor: 1 Stirrer bar,
2 Still pot (the still pot should
not be overfilled and the
volume of solvent in the still pot
should be 3 to 4 times the
volume of the soxhlet
chamber), 3 Distillation path, 4
Thimble, 5 Solid, 6 Siphon top, 7
Siphon exit, 8 Expansion
adapter, 9 Condensor, 10
Cooling water in, 11 Cooling
water out
Some extraction methods
Organic species
“like dissolves like”
Ionizing organic species
Limit ionization by controlling pH
Use of organic complexing reagents.
Many reagents available to complex metal ions - more soluble in
organic phase
Ion-association complexes
Formation of neutral ion pairs.
Solvent Removal Methods
Once the solute is extracted into the extraction solvent, it
generally must be isolated from the solvent.

Several methods are used to remove the solvent:

1. Distillation can be quite efficient.
2. Evaporation
3. Precipitation
and further decanting or filtering. Usually results in low
yields.
Solvent Removal Methods
4. Adsorption
onto a suitable stationary phase is desirable especially
if additional solute purification is needed.
5. Back-extraction
needs additional purification using a third extracting
solvent
or
an extraction back into the original feed solvent (for
liquid systems) through changes in the distribution
ratio by adjusting parameters such as pH.