CHEM 340
At the end of this lecture you should be able to:
✓ Differentiate between liquid-liquid and solid-liquid extraction
processes.
✓ Explain with reasoning the requirements for the extraction solvent
that leads to effective extraction.
✓ Use distribution coefficient to indicate whether the compounds are
mainly distributed in the organic or aqueous phase after
extraction.
✓ Note the effect of single versus successive extraction.
✓ Calculate the amount of analyte remaining in the aqueous phase
after extraction.
• It is a technique used to separate a desired
compound from a mixture.
There are two types of extraction process:
✓ Solid - Liquid Extraction
✓ Liquid - Liquid Extraction
• Removal of a compound from a solid via a liquid
extraction media.
• The desired compound diffuses from its natural solid
form into the solvent.
• The transfer of a compound from one liquid phase
(aqueous) into another liquid phase (organic).
• The separation of the compounds depends upon
the unequal distribution of the compounds between
the immiscible liquids.
✓ Should be immiscible in water: if solvent is miscible, the
recovery of solvent is required and it needs extra costs.
✓ Should be selective: ability to remove and concentrate
the analyte from the other components in water.
✓ Density differential: small difference in density of solvent
and water causes separation problems, lower capacity.
✓ Should have minimal viscosity: too viscous solvent inhibit
mass transfer.
✓ Should not be expensive and explosive
✓ Shaking - Establish equilibrium concentration of solute
between the two immiscible solvents.
✓ Venting - Release pressure build-up.
✓ Separating layers
Always remove bottom layer through the bottom
✓ Allow time to separate
Drain some, repeat to get all of the solvent
✓ Drying - Remove traces of water from organic solvent.
✓ Remove solvent - Isolate extracted compound.
• It is the ratio of concentrations of a compound in a
mixture of two immiscible phases at equilibrium.
• These coefficients are a measure of the difference in
solubility of the compound in these two phases.
[A] organic
KD =[A]aqueous
KD < 1 The substance is mostly in H2O
KD = 1 The substance is mostly in Both
KD > 1 The substance is mostly in Organic
Example:
An extraction of 100 mL of 10.0 mmol herbicides was
carried out with 30 mL of methanol. After extraction, 2.50
mmol of herbicides remained in the aqueous layer.
Calculate KD
KD = [A] organic
[A]aqueous
= 7.50 mmol / 30 mL
2.50 mmol / 100 mL
= 10.0
An extraction of 100 mL of 10.0 mmol herbicides was
carried out with methanol, Kd = 10.0.
Calculate the total amount of herbicides extracted by:
a) 30 mL
b) Two 15 mL portions.
KD = 10.0 = X mmol in methanol / 15 mL
(10.0 - X) mmol in water / 100 mL
KD = 10.0 = X mmol in methanol / 30 mL X = 6.0 mmol in methanol (end of 1st
(10.0 - X) mmol in water / 100 mL extraction)
X = 7.50 mmol in methanol KD = 10.0 = __X' mmol in methanol / 15 mL___
(4.0 - X') mmol in water / 100 mL
X' = 2.4 mmol in methanol (by 2nd extraction)
X + X' = 8.4 mmol in methanol by both
extractions
8.4 mmol in methanol compared to 7.5 mmol
in methanol
• Fraction remaining in a phase, q
𝑽𝒂𝒒 𝒏
𝒒= qaq + qorg = 1
𝑽𝒐𝒓𝒈𝑲𝒅 + 𝑽𝒂𝒒
• % Extraction Efficiency
A 100.00 mL wastewater sample containing 0.100 M
herbicides was extracted using 30.00 mL of methanol (KD =
10.00).
Calculate the extraction efficiency.
𝒏
𝑽𝒂𝒒
𝒒=
𝑽𝒐𝒓𝒈𝑲𝒅+𝑽𝒂𝒒
𝟏
𝟏𝟎𝟎 𝒎𝑳
q=
𝟑𝟎 𝒎𝑳 𝒙 𝟏𝟎.𝟎𝟎+𝟏𝟎𝟎 𝒎𝑳
= 0.25
%E = 100(1-qn) = 100(1-0.251) = 75.0%
Calculate the volume of methanol (KD =10.00) that should
be used to extract a 100.00 mL wastewater sample
containing 0.100 M herbicides so that the %E is 95.0%.
%E = 100(1 – qn),
therefore q = 0.050
𝒏
𝑽𝒂𝒒
q=
𝑽𝒐𝒓𝒈𝑲𝒅+𝑽𝒂𝒒
𝟏
𝟏𝟎𝟎 𝒎𝑳
0.050 =
𝑽𝒐𝒓𝒈 𝒙 𝟏𝟎.𝟎𝟎+𝟏𝟎𝟎 𝒎𝑳
= 190 mL
Calculate the number of 30.00 mL extractions of methanol
(Kd = 10.00) that should be used to extract a 100 mL
wastewater sample containing 0.100 M PAHs so that the %E
is 95.0%.
%E = 100(1 – qn),
therefore q = 0.050
𝒏
𝑽𝒂𝒒
𝒒=
𝑽𝒐𝒓𝒈𝑲𝒅+𝑽𝒂𝒒
If %E is 95.0%, then q = 0.050
𝑽𝒂𝒒 𝒏
𝒒=
𝑽𝒐𝒓𝒈𝑲𝒅 + 𝑽𝒂𝒒
𝟏𝟎𝟎 𝒎𝑳 𝒏
0.050 =
𝟑𝟎 𝒎𝑳 𝒙 𝟏𝟎. 𝟎𝟎 + 𝟏𝟎𝟎 𝒎𝑳
0.050 =0.25n
log 0.050 = n log 0.25
n = 2.16
Therefore 2 extractions will give you a 95.0% recovery with 30 mL aliquots of
methanol.
The distribution constant for iodine between an organic
solvent and H2O is 10. Find the concentration of I2
remaining in the aqueous layer after extraction of 100.0
mL of 2.00 x 10-4 M I2 with the following quantities of the
organic solvent of 30.0 mL
𝑽𝒂𝒒 𝒊
𝑨𝒊= 𝑨 𝟎
𝑽𝒐𝒓𝒈𝑲𝒅 + 𝑽𝒂𝒒
100 𝑚𝐿 1
[I2] = x 2.00 x 10−4 M =5.0 x 10−5 M
30 𝑚𝐿 𝑥 10.00 + 100 𝑚𝐿
