p
What are Phase Separations? Partition Equilibrium Theory Competing Equilibria and the Distribution Ratio Extraction Efficiency Separation Efficiency Solid Phase Extraction
www.chem.unsw.edu.au/UGNotes/Guilhaus/
CHEM2801 Analytical & Physical Chemistry for Food Science - Separations -1 1
Vaq
KD
Vorg
D
q
They rely on the analyte being more soluble in an immiscible or immobilised phase. Liquid-liquid and liquid-solid phase extractions are important in: Sample clean-up Sample preconcentration
C6H5COOH(aq)
example
C6H5COOH(org)
Kd =
[C 6 H 5COOH]org [C 6 H 5COOH]aq
Competing Equilibria
Solutes often participate in other equilibria in both phases. Consider benzoic acid (C 6H5COOH = HA)
Kdim
HA2(org)
Ka
A-(aq) + H3O+
Distribution Ratio
The distribution ratio (D) measures the relative molar concentration of analyte (in all its forms) in the two phases
Consider the previous example of benzoic acid (C6H5COOH = HA)
D=
Corg Caq [HA]org + 2[(HA )2 ]org + [A ]org [HA]aq + 2[( HA )2 ]aq + [ A ]aq
M. Guilhaus UNSW 1999 - All rights reserved.
D=
Kdim
(HA)2(org)
Ka
A-(aq) + H3O+
Distribution Ratio
Which concentration terms in the D equation will be negligible? Under what pH conditions will the value of D be highest in this example?
D=
Corg Caq [HA]org + 2[(HA )2 ]org + [A ]org [HA]aq + 2[( HA )2 ]aq + [ A ]aq
M. Guilhaus UNSW 1999 - All rights reserved.
D=
Kdim
(HA)2(org)
Ka
A-(aq) + H3O+
Distribution Ratio
The distribution ratio is a quantitative measure of how a solute partitions between two immiscible solvents.
M. Guilhaus UNSW 1999 - All rights reserved.
Efficiency of Extraction
It is important to know and control how much analyte will be recovered in an extraction. Normally we aim at 99.9% or more for quantitative analysis For a single extraction it is easy to predict efficiency as a function of D and the volumes of the organic and aqueous phases.
M. Guilhaus UNSW 1999 - All rights reserved.
CorgVorg
EQUILIBRIUM
CinVaq
CaqVaq
p q
8
Efficiency of Extraction
p q
p is the fraction of analyte (any form) transferred to the organic phase after equilibration q is the fraction of analyte (any form) left in the aqueous phase after equilibration
p=
q=
CorgVorg
EQUILIBRIUM
CinVaq
CaqVaq
p=0.83 (83% Cl 2 transferred to organic phase) q=0.17 (17% Cl 2 remains in aqueous phase)
(b) 500mL of CCl4
100 mL 1 q = 0.02
p=0.98 (98% Cl 2 transferred to organic phase) q=0.02 (2% Cl 2 remains in aqueous phase)
500 mL
p = 0.98 0
10
p = 0.98 0
11
Bad for health and safety of lab staff Usually a fire hazard Usually impractical because or sze and weight of apparatus.
What is a better way to improve efficiency without using large amounts of solvent?
CHEM2801 Analytical & Physical Chemistry for Food Science - Separations -1 12
1 2 3
q pq q2
p + pq
Successive extractions improve recovery efficiency with smaller total amount of solvent
pq2 p+pq+pq2
q2
0
pqn-1
qn-1
qn
p+pq+pq2++pqn-1
13
p= p=
71.4% (100p) Cl2 removed to organic phase 28.6% (100q) remains in aqueous
Second Extraction
71.4% of 28.6% = 20.4% of Cl2 extracted into organic phase Total extracted = 91.8% (71.4% + 20.4%) c.f. 83% for single 50 mL step
CHEM2801 Analytical & Physical Chemistry for Food Science - Separations -1 14
Clue: change the volume ratio Clue: Change the value of D by adjusting the pH
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Separating Solutes
We have seen how successive extractions improve recovery efficiency. What if we have two solutes that extract so that one has a much higher D than the other. Will successive extractions help us to remove the more extractable solute from the less extractable one?
Example:
Separating Solutes
Example (contd):
Extraction 1: 99% A extracted; 9.1% B extracted A is 100[B]/[A] = 9.2% contaminated with B Extraction 2: 99.99% of A extracted; 17% B extracted
M. Guilhaus UNSW 1999 - All rights reserved.
18
98% (99% of 99%) of A remains in organic phase 0.83% (9.1% of 9.1%) of B remains in organic phase Extract of A is now (100[B]/[A] = 100(0.83)/(98) = 0.85% contaminated with B.
Countercurrent fractionation improves separation (selectivity) but some recovery efficiency is lost
CHEM2801 Analytical & Physical Chemistry for Food Science - Separations -1 19
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