Principle of Extraction (Overview)
Principle of Extraction (Overview)
Principle of Extraction (Overview)
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
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
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
+
=
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)
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
Unattended operation
Unattended operation
Extract low K
Extract low K
D D
Time (18
Time (18
-
-
24 hours)
24 hours)
[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
+ +
=