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Supercritical fluids
Relatively new technique as aninstrumental method.First suggested by Lovelock in 1958.First commercial instruments
!
1981 - packed columns
!
1985 - capillary columns
Supercritical fluids
Two types of applicationsSupercritical fluid extraction (SFE)Supercritical fluid chromatography (SFC)As a chromatographic method, it fitssomewhere between HPLC and GC.
!
- offers advantages of each.
Supercritical fluid advantages
As a chromatographic method
•
can use low temperatures for separation
•
can use packed or capillary columns
•
pressure and polarity of mobile phase can be‘tuned’ for optimum separationAs an extraction method
•
can also be ‘tuned’
•
removal of extracting solvent is very easy
Supercritical fluid disadvantages
More expensive equipmentIncreased development time - more factorsto control means more to optimize.Methods not as developed as GC or HPLC.
!
- not as many applications (yet)
What is a supercritical fluid?
Above a certain temperature, a vapor can nolonger be liquefied regardless of pressure
!
critical temperature - T
c
supercriticalfluid region
T
c
solidliquidgasP
c
temperature
  p  r  e  s  s  u  r  e
Examples
Fluid
!!
T
c
,
o
C
!!
P
c
, atm density
*
CO
2
!!
 
31.3
!!
72.9
!!
0.96N
2
O
!!
 
36.5
!!
72.5
!
 
!
0.94NH
3
!!
132.5 112.5
!!
0.40n-C
5
!!
196.6
!!
33.3
!!
0.51n-C
4
!!
152.0
!!
37.5
!!
0.50CCl
2
F
2
!
111.8
!
40.7
!
 
!
1.12CHF
3
!!
 
25.9
!!
46.9
!
 
!
-----
*
density in g/ml at 400 atm
 
Supercritical fluids
These fluids have densities anddiffusivities similar to liquids butviscosities comparable to gases.
mobile density
!
viscosity
!
diffusivityphase
!
(g/ml)
!
(poise)
!
(cm
2
/sec)gas
!
~10
-3
!
0.5 - 3.5 (x10
-4
) 0.01 - 1.0SCF
!
0.2-0.9 0.2 - 1.0 (x10
-3
) 0.1 - 3.3 (x10
-4
)liquid
!
0.8-1.0 0.3 - 2.4 (x10
-2
) 0.5 - 2.0 (x10
-5
)
Supercritical fluids
This means that it is possible to developmethods that offer:flows similar to GC base methods -due to low viscosityefficiencies similar to HPLCmethods - due to low diffusion.
Supercritical fluid extraction
With normal solvent extraction methods, solutesthat have low extraction efficiencies require:Batch extractionsUse of large amount of solvent followedby solvent removal.Continuous extractionHeating of sample/solvent mixture.Both require heating of the solute and someventing of the solvent to the atmosphere.
Supercritical fluid extraction
With SFECan do a continuous extractionRemove solvent simply by ventingUse non-toxic, inexpensive solventsControl nature of extraction byusing various pressuresadding ‘modifying’ materials tosupercritical fluid
pumpSFCfluidmodifierfluidsextractionthimblecollectiontrapventrestrictornozzle
Supercriticalfluid extraction
Supercritical fluid extraction
Most commonly used solvent is CO
2
!
- inexpensive
!
- non-toxic
!
- low critical temperature (31.3
o
C)Common modifiers include
!
HCl
!
make the solvent acidic.
!
NH
3
!
makes the solvent basic.This allows a separation to target specific typesof materials
 
Supercritical fluid extraction
•
Pressure can also be used to controlextraction.
•
Increasing pressure will increasedensity.
•
Easily extracted materials will beextracted at lower densities.
•
Raising the pressure can be used toextract materials with lower extractionefficiency.
•
The temperature of the extractionthimble can also be optimized.
Supercritical fluid extraction
Example - pesticide analysis.Chromatograms obtained for two soil extracts.extraction at 100barextraction at 300bar2,4,5-T2,4,5-T
2,4,5-T - trichlorophenoxyacetic acid
Supercritical fluid extraction
   %   r  e  c  o  v  e  r  y
100
 
80
 
60
 
40
 
20
 
050 100 150 200 250 300
Recovery of 2,4,5-T
Pressure can be used to alter the extractionefficiency.This allows for complex samples to beextracted into groups.
Supercritical fluid chromatography
Supercritical fluid extraction shows that wecan control how a solute interacts with a mobilephase. By introducing a stationary phase, wecan start doing chromatographyFactors we can control- pressure of mobile phase- temperature- nature of solvent (Snyder selectivity)- stationary phase type
Supercritical fluid chromatography
150,000100,00050,0001.0 1.1 1.2
!
, selectivity
capillaryGCHPLCSFC
Number of plates required to achieve aseparation with R
S
= 1.5 and k’ = 2
Supercritical fluid chromatograph
pumpsystem
  p  r  o  g  r  a  m  m  e  r
pressuretransducercolumninjectionvalvesolventpreheaterovendetectorrestrictorvent
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