Principle of Extraction (Overview)

Download as pdf or txt
Download as pdf or txt
You are on page 1of 36

1 1

Principle of Extraction
Principle of Extraction
(Overview)
(Overview)
Extraction of
Extraction of
Semivolatile
Semivolatile
Organics from Liquids
Organics from Liquids
2 2
Extraction
Extraction
Chemical properties of the analytes and liquid
Chemical properties of the analytes and liquid
medium
medium
Vapor pressure Vapor pressure
Solubility Solubility
Molecular weight Molecular weight
Hydrophobicity Hydrophobicity
Acid dissociation Acid dissociation
Extractants
Extractants
Gas Gas
Liquid Liquid
Supercritical fluid Supercritical fluid
Solid Solid
Transport of chemicals
In human body
In the air-water-soil
environment
Between immiscible phases
X
A
X
B
[ ]
[ ]
A
B
D
X
X
K =
Chemical Equilibrium Chemical Equilibrium
3 3
Volatilization
Volatilization
Henry
Henry

s Law Constant: Volatility from the


s Law Constant: Volatility from the
solution into air
solution into air
Vapor Pressure: Volatility from the pure
Vapor Pressure: Volatility from the pure
substance into the atmosphere
substance into the atmosphere
[ ]
[ ]
Solubility
Pressure Vapor
H
X
X
K H'
L
G
D
=
= =
4 4
Categorization of Vapor Pressure
Categorization of Vapor Pressure
and Solubility
and Solubility
Vapor pressure
Vapor pressure

Low:
Low:
1x10
1x10
- -6 6
mmHg
mmHg

Medium
Medium
1x10
1x10
- -6 6

1x10
1x10
- -2 2
mmHg
mmHg

High
High
> 1x10
> 1x10
- -2 2
mmHg
mmHg
Solubility
Solubility

Low:
Low:
<10 ppm
<10 ppm

Medium
Medium
10
10

1000 ppm
1000 ppm

High
High
> 1000 ppm
> 1000 ppm
5 5
Henry
Henry

s Law Constant vs. Extraction techniques


s Law Constant vs. Extraction techniques
H
H
analyte analyte
<
<
H
H
solvent solvent
Solute =
Solute =
nonvolatile in the
nonvolatile in the
solvent,
solvent,
preconcentration
preconcentration
H
H
analyte analyte
>
>
H
H
solvent solvent
Solute =
Solute =
semivolatile
semivolatile
to
to
volatile in the
volatile in the
solvent
solvent
P
v
a
p
S
H
i
g
h

H
L
o
w

H
Low
High Medium
L
o
w
H
i
g
h
M
e
d
i
u
m
6 6
Organic Solute in Water
Organic Solute in Water
Nonvolatile: unimportant
Nonvolatile: unimportant
H < 3x10
H < 3x10
- -7 7
atm.m
atm.m
3 3
/mol
/mol
Semivolatile
Semivolatile
: slowly
: slowly
3x10
3x10
- -7 7
< H < 10
< H < 10
- -5 5
atm.m
atm.m
3 3
/mol
/mol
Volatile: significant
Volatile: significant
10
10
- -5 5
< H < 10
< H < 10
- -3 3
atm.m
atm.m
3 3
/mol
/mol
Highly volatile: rapid
Highly volatile: rapid
H > 10
H > 10
- -3 3
atm.m
atm.m
3 3
/mol
/mol
7 7
Hydrophobicity
Hydrophobicity
n
n
-
-
octanol/water
octanol/water
partition coefficient
partition coefficient

Highly hydrophilic: log


Highly hydrophilic: log
K
K
ow ow
< 1
< 1

Highly hydrophobic: log


Highly hydrophobic: log
K
K
ow ow
> 3
> 3
-
-
4
4
[ ]
[ ]
w
o
ow
X
X
K =
8 8
Acid
Acid
-
-
base Equilibria
base Equilibria
HA
HA

H
H
+ +
+ A
+ A
- -
Buffer
Buffer
pH =
pH =
pK
pK
a a
+ 2
+ 2
[ ] [ ]
[ ] HA
A H
K
-
a
+
=
[ ]
[ ] HA
A
log pK pH
-
a
+ =
9 9
Sample Prep
Sample Prep

Aqueous
Aqueous
Sample
Sample
Liquid
Liquid
-
-
Liquid Extraction (LLE)
Liquid Extraction (LLE)
Solid
Solid
-
-
Phase Extraction (SPE)
Phase Extraction (SPE)
Solid Phase
Solid Phase
Microextraction
Microextraction
(SPME)
(SPME)
Stir Bar
Stir Bar
Sorptive
Sorptive
Extraction (SBSE)
Extraction (SBSE)
Liquid
Liquid
-
-
Phase
Phase
Microextraction
Microextraction
(LPME)
(LPME)
10 10
Liquid
Liquid

Liquid
Liquid
Extraction
Extraction
LLE
LLE
11 11
Solvent Extraction
Solvent Extraction
-
-
LLE
LLE
Popular technique
Popular technique
For non
For non
-
-
semi volatile organic compounds
semi volatile organic compounds
Partitioning the sample between two
Partitioning the sample between two
immiscible phases
immiscible phases

Aqueous phase: Sample matrix


Aqueous phase: Sample matrix

Organic phase: Organic solvent


Organic phase: Organic solvent
Like dissolves like
Like dissolves like
A(aq) A(org)
13 13
LLE
LLE
-
-
Basic Theory
Basic Theory
Distribution Coefficient (K
d
)
K
d
is constant at a particular temperature
[ ]
[ ]
aq
org
D
A
A
K =
14 14
Separation by extraction
Separation by extraction
Distribution equilibrium
Distribution equilibrium
Partition of solute between two immiscible
Partition of solute between two immiscible
phases
phases
A
aq
A
org
aq
org
aq A
org A
] A [
] A [
) a (
) a (
K =
o
i
aq org
aq
i
] A [
V K V
V
] A [

+
=
15 15
Example
Example
K of I K of I
2 2
between organic solvent and H between organic solvent and H
2 2
O = 85. Find [I O = 85. Find [I
2 2
] ]
remaining in the aqueous layer after extraction of 50.0 remaining in the aqueous layer after extraction of 50.0
mL of 1.00 x 10 mL of 1.00 x 10
- -3 3
M I M I
2 2
with organic solvent of a) 50.0 mL, with organic solvent of a) 50.0 mL,
b) 2 x 25.0 mL, c) 5 x 10.0 mL b) 2 x 25.0 mL, c) 5 x 10.0 mL
M 10 16 . 1 10 00 . 1
0 . 50 ) 85 0 . 50 (
0 . 50
] [I ) a
5 3
1
1 2

=

+
=
M 10 28 . 5 10 00 . 1
0 . 50 ) 85 0 . 25 (
0 . 50
] [I ) b
7 3
2
2 2

=

+
=
M 10 29 . 5 10 00 . 1
0 . 50 ) 85 0 . 10 (
0 . 50
] [I ) a
10 3
5
5 2

=

+
=
16 16
LLE
LLE
-
-
Basic Theory
Basic Theory
The fraction of analyte extracted (
The fraction of analyte extracted (
E
E
) or
) or
Recovery (R)
Recovery (R)
( )
( ) V K 1
V K
R E
V C V C
V C
R E
D
D
aq aq o o
o o
+
= =
+
= =
V = Phase ratio; V
o
/V
aq
17 17
LLE
LLE
-
-
Basic Theory
Basic Theory
Distribution Ratio (D)
Distribution Ratio (D)

If the analyte is partially dissociated in


If the analyte is partially dissociated in
solution and exist as neutral species, free
solution and exist as neutral species, free
ions, ion
ions, ion
-
-
paired with counter ion
paired with counter ion

Using D for K
Using D for K
D D
phase aqueous the in forms chemical all in X of Conc.
phase organic the in forms chemical all in X of Conc.
D=
18 18
LLE
LLE
10
10
-
-
1000 mL
1000 mL
Phase ratio; 0.1 < V < 10
Phase ratio; 0.1 < V < 10
One
One
-
-
step extraction;
step extraction;
K
K
d d
must be large, >10
must be large, >10
K K
Ow Ow
(log (log K K
Ow Ow
) ) Octanol Octanol- -water partition coefficient water partition coefficient
2
2
-
-
3 repeat extractions are required for
3 repeat extractions are required for
quantitative recoveries
quantitative recoveries
( )
n
D
V K 1
1
- 1 E

+
=
19 19
How many extraction will be necessary?
How many extraction will be necessary?
K
D
= 10
V = 10
#1 E = 99.0%
K
D
= 10
V = 1
#1 E = 90.9%
#2 E = 99.2%
K
D
= 10
V = 0.1
#1 E = 50.0%
#2 E = 75.0%
#3 E = 87.5%
#4 E = 93.8%
#5 E = 96.9%
#6 E = 98.4%
#7 E = 99.2%
K
D
= 1000
V = 0.1
#1 E=99.0%
K
D
= 100
V = 1
#1 E=99.0%
20 20
How many extraction will be necessary?
How many extraction will be necessary?
Typically, aqueous phase > organic phase
Typically, aqueous phase > organic phase

V = 0.05
V = 0.05
-
-
0.1 (50:1000, 100:1000)
0.1 (50:1000, 100:1000)
Multiple extractions are more efficient
Multiple extractions are more efficient
K
D
= 1000
V = 0.1
#1 E = 99.0%
K
D
= 1000
V = 0.05
#1 E = 98.0%
#2 E = 99.9%
K
D
= 100
V = 0.05
#1 E = 83.3%
#2 E = 97.2%
#3 E = 99.5%
21 21
Single vs. Multiple Extraction
Single vs. Multiple Extraction
99.999 99.999 0.038 0.038 98.039 98.039 99.961 99.961 1.922 1.922 98.039 98.039 98.039 98.039 99.338 99.338
1000 1000
48.800 48.800 12.800 12.800 20.000 20.000 36.000 36.000 16.000 16.000 20.000 20.000 20.000 20.000 42.857 42.857
5 5
97.671 97.671 5.832 5.832 71.429 71.429 91.839 91.839 20.411 20.411 71.429 71.429 71.429 71.429 88.235 88.235
50 50
99.538 99.538 2.315 2.315 83.333 83.333 97.223 97.223 13.890 13.890 83.333 83.333 83.333 83.333 93.750 93.750
100 100
99.993 99.993 0.142 0.142 96.154 96.154 99.851 99.851 3.697 3.697 96.154 96.154 96.154 96.154 98.648 98.648
500 500
Cum. Cum.
%E %E
Add Add
%E %E
3 3
rd rd
%E %E Cum. %E Cum. %E
Add. Add.
%E %E
2 2
nd nd
%E %E %E %E %E %E
3x50 mL 3x50 mL
1x50 1x50
mL mL
1x50 mL 1x50 mL 2x50 mL 2x50 mL
1x50 1x50
mL mL
1x50 1x50
mL mL
3 3
rd rd
extraction extraction 2 2
nd nd
extraction extraction
Single Single
1x50 mL 1x50 mL
V=20 V=20
Single Single
1x150 mL 1x150 mL
V=6.67 V=6.67
K K
D D
22 22
LLE
LLE
The net amount of analyte extracted depends on
The net amount of analyte extracted depends on
the K
the K
D D
The net amount of analyte extracted depends on
The net amount of analyte extracted depends on
the
the
V
V
org org
/V
/V
aq aq
More analyte is extracted with multiple portions of
More analyte is extracted with multiple portions of
extracting solvent than single portion of an
extracting solvent than single portion of an
equivalent volume of the extracting phase
equivalent volume of the extracting phase
Recovery is independent of the concentration of
Recovery is independent of the concentration of
the original aqueous sample
the original aqueous sample
23 23
Selection of Extraction Solvents
Selection of Extraction Solvents
Immiscible with water (Low solubility)
Immiscible with water (Low solubility)
Have polarity and H
Have polarity and H
-
-
bonding for good
bonding for good
recovery of analytes (organic phase)
recovery of analytes (organic phase)
Volatile for easy removal after extraction
Volatile for easy removal after extraction
(pre
(pre
-
-
concentration if necessary)
concentration if necessary)
Compatible with method of analysis
Compatible with method of analysis

GC
GC

RP
RP
-
-
HPLC
HPLC
24 24
Solvent Modification
Solvent Modification
Selectivity can be influenced by choices of
Selectivity can be influenced by choices of
additives affecting the equilibrium process
additives affecting the equilibrium process

Adjusting pH
Adjusting pH

Ion pair
Ion pair

Chelating agent
Chelating agent

Salting out
Salting out
Increase K
D
in
organic phase
25 25
Example
Example
Extraction of amine (Aniline) from aqueous
Extraction of amine (Aniline) from aqueous
sample
sample

Buffer solution at least 1.5 pH units higher


Buffer solution at least 1.5 pH units higher
than its
than its
pK
pK
a a
, Amine will become un
, Amine will become un
-
-
ionized
ionized
and will be extracted into the organic phase
and will be extracted into the organic phase
NH
3
+
+ H
2
O
NH
2
+ H
3
O
+
pK
a
= 4.6
26 26
Typical Solvents used in LLE
Typical Solvents used in LLE
Aqueous solvent
Aqueous solvent
Pure water Pure water
Acidic solution Acidic solution
Basic solution Basic solution
High salt (Salting out) High salt (Salting out)
Complexing Complexing agents agents
(ion (ion- -pairing, chelating pairing, chelating
and and chiral chiral agents) agents)
Combination of two or Combination of two or
more above more above
Water immiscible
Water immiscible
organic solvent
organic solvent
Diethyl ether Diethyl ether
Methylene Methylene chloride chloride
Chloroform Chloroform
Ethyl acetate Ethyl acetate
Aliphatic Aliphatic ketones ketones (C6+) (C6+)
Aliphatic alcohol (C6+) Aliphatic alcohol (C6+)
Toluene and Toluene and xylenes xylenes
Combination of two or Combination of two or
more above more above
27 27
Emulsion
Emulsion
Small droplets of organic phase floating in the
Small droplets of organic phase floating in the
immiscible aqueous phase
immiscible aqueous phase
Where the mass transfer occurs
Where the mass transfer occurs
Vigorous shaking allows thorough interspersion
Vigorous shaking allows thorough interspersion
between two immiscible phases; high efficiency
between two immiscible phases; high efficiency
Emulsion must be broken before collection
Emulsion must be broken before collection
Sample containing surfactants or fatty materials
Sample containing surfactants or fatty materials
slow breaking or incomplete breaking of emulsion slow breaking or incomplete breaking of emulsion
28 28
Breaking Emulsions
Breaking Emulsions
Add salt to aqueous phase
Add salt to aqueous phase
Use a heating
Use a heating
-
-
cooling extraction vessel
cooling extraction vessel
Filter emulsion through a glass wool plug
Filter emulsion through a glass wool plug
Filter the emulsion through phase
Filter the emulsion through phase
separation filter paper
separation filter paper
Centrifuge
Centrifuge
Add a small amount of a different organic
Add a small amount of a different organic
solvent
solvent
29 29
Continuous LLE
Continuous LLE
K
K
D D
is very small
is very small
Kinetics of the extraction is slow
Kinetics of the extraction is slow
Sample is large, requiring too many
Sample is large, requiring too many
extractions
extractions
Fresh organic solvent is recycled
Fresh organic solvent is recycled
continuously in the form of droplets
continuously in the form of droplets
passing through the sample aqueous
passing through the sample aqueous
phase
phase
30 30
Continuous LLE
Continuous LLE
G. LeBlanc, LC-GC, 19(11), 1120-1130 (2001)
Solvent heavier than water Solvent heavier than water Solvent lighter than water Solvent lighter than water
31 31
Continuous LLE
Continuous LLE
-
-
Solvent heavier than water
Solvent heavier than water
32 32
Continuous LLE
Continuous LLE
-
-
Solvent lighter than water
Solvent lighter than water
33 33
Continuous LLE
Continuous LLE
Advantage
Advantage

Unattended operation
Unattended operation

Extract low K
Extract low K
D D

Relatively low solvent usage


Relatively low solvent usage

Excellent extraction efficiency


Excellent extraction efficiency
Disadvantage
Disadvantage

Time (18
Time (18
-
-
24 hours)
24 hours)

Very volatile compounds can be lost


Very volatile compounds can be lost

Thermally unstable compounds can be


Thermally unstable compounds can be
degraded
degraded
34 34
Disadvantage of LLE
Disadvantage of LLE
Time required; several successive extractions
Time required; several successive extractions
Seldom complete
Seldom complete
Use and disposal of large volumes of toxic
Use and disposal of large volumes of toxic
organic solvents
organic solvents
Formation of emulsion; hard to break emulsion
Formation of emulsion; hard to break emulsion
Cumbersome glassware
Cumbersome glassware
Labor
Labor
-
-
intensive
intensive
Sample
Sample
preconcentration
preconcentration
is often required
is often required
Not easily automated
Not easily automated
Cost
Cost
35 35
Extracting inorganic species
Extracting inorganic species
Separating metals ions as
Separating metals ions as
chelates
chelates

Organic chelating agents react with metals to


Organic chelating agents react with metals to
form uncharged complexes that are highly
form uncharged complexes that are highly
soluble in organic solvents
soluble in organic solvents
2H
+
+ 2Q
-
+ M
2+
MQ
2
MQ
2
2HQ
2HQ
Organic phase
Aqueous phase
Q = 8-hydroxyquinoline
36 36
Extracting inorganic species
Extracting inorganic species
Overall equilibrium
2HQ (org) + M
2+
(aq) MQ
2
(org) + 2H
+
(aq)
aq
2 2
org
2
aq org 2
] [M [HQ]
] [H ] [MQ
K
+
+
=

[HQ]
org
is present in large excess with respect to [M
2+
]
aq
aq
2
2
aq org 2 2
org
] [M
] [H ] [MQ
K [HQ] K
+
+
= =

2
aq aq
2
org 2
] [H
K
] [M
] [MQ
+ +
=
37 37
Extracting inorganic species
Extracting inorganic species
Ratio of concentration of metal species in the two layers Ratio of concentration of metal species in the two layers
is inversely proportional to [H is inversely proportional to [H
+ +
] ]
2 2
aq aq
K varies from metal ion to metal ion, makes it possible to K varies from metal ion to metal ion, makes it possible to
selectively extract one selectively extract one cation cation from another by buffering from another by buffering
aqueous solution aqueous solution
2
aq aq
2
org 2
] [H
K
] [M
] [MQ
+ +
=

You might also like