Chemosphere 43 (2001) 123135

Advances with supercritical uids [review]

Werner H. Hauthal
Wilhelm-Ostwald-Institut f
ur Physikalische und Theoretische Chemie, Universit
at Leipzig, Johannisallee 29, D-04103 Leipzig, Germany

Abstract
In the last decade, supercritical uids more and more have been proved as environmentally benign media for
chemical and related processes. Many new processes and products have been developed, using the inherent physical and
chemical properties of supercritical uids. Moreover, these processes also promise economic eects. The prerequisites
for this success however, are a sound knowledge of physico-chemical properties of and phenomena in supercritical
mixtures and the availability of other chemical engineering data. This requires an eective exchange of knowledge
between a large number of branches of science. In the following, a lot of recent papers will be cited, which should give
an overview of actual results on fundamentals and their applications. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Sustainable chemistry; Supercritical uids; Fluid phase equilibria; Phenomenology; Solvatochromism; Models; Equations
of state; Chemical engineering data; Supercritical uid extraction; Chemical syntheses and reactions; Materials processing; Dyeing;
Review

1. Introduction
In the following, an overview of more recent publications on applications of supercritical uids in chemistry and chemical engineerig technologies is given in a
tabular form (titles of the publications with some explaining key words; the keywords also outline the relations to related topics). Using supercritical uids is one
possibility to carry out chemistry and chemical technologies in a sustainable manner (``green chemistry'').
Supercritical CO2 (or other supercritical uids) are an
environmentally benign alternative to conventional industrial solvents. Among others, they oer possibilities
to reduce the size of reactor volumes to a great extent,
and to accelerate chemical processes. The rapid expansion of supercritical solutions (RESS) process, e.g., allows the production of powders with a narrow
distribution curve of the (therefore well dened) particle
sizes, what is very important for the applications of
those powders in several industrial branches.
In Section 2 some papers are cited, which underline
the signicance of supercritical uids for a sustainable
chemistry. Furthermore, some references referring to
research activities in the US, Japan and Germany. In the

Sections 3.1 to 3.5 attention will be paid to the scientic

fundamentals for using supercritical uids (phenomenology, theories, and chemical engineering data). It
should be underlined, that chemical mixtures under supercritical conditions may have some more components
(supercritical uid, modier), much more extented
ranges of temperature, pressure (density), and much
more complicated phase diagrams, as well as novel
phenomenological eects. In this context, the further
development of global phase diagrams deserves attention as basis of any reliable development of chemical
engineering applications (syntheses, separation operations and others).
The recent development of solvent databases, other
chemical engineering data and computational methods
as aids in the selection and/or design of feasible or optimal environmentally benign solvent alternatives for
specic applications is another prerequisite. Papers
dealing with experimental results and calculation methods are cited in Sections 4.1 to 4.3.
The Sections 5.1 and 5.2 should give some impressions of the applications of supercritical uids in the
chemical engineering practice in dierent branches of
industry (e.g., chemistry, environmental, textile nishing

0045-6535/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 0 ) 0 0 3 3 2 - 5

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W.H. Hauthal / Chemosphere 43 (2001) 123135

Abbreviatiions
AOT
ASE
cmc
e.o.s.
GPD
LLE
LSER
MC
MD
Mdif
MS
NMR
PAH
PCBs
PDMS

sodium bis(2-ethylhexyl) sulfosuccinate

accelerated solvent-extraction
critical micelle concentration
equation of state
global Phase Diagram(s)
liquidliquid equilibrium (equilibria)
linear solvation energy relationship
MonteCarlo (simulations)
molecular dynamics
molecular-diusion
Mass spectrometry
nuclear magntic resonance
polycyclic aromatic hydrocarbons
polychlorinated biphenyls
poly(dimethylsiloxane)

and dyeing). Concerning syntheses in supercritical uids

and analytical methods, however, the monograph of
Jessop and Leitner (Jessop and Leitner, 1999) is recommended for more extensive information.
2. Green chemistry/sustainable chemistry with supercritical uids. Research activities
2.1. Reviews and some recent conference reports
Supercritical uids: Clean solvents for green chemistry (in German: ``Nachhaltige Chemie'') (Poliako
et al., 1999);
Supercritical carbon dioxide: The ''greener'' solvent
(Black, 1996);
Solvents Molecular trees for green chemistry (Brennecke, 1997);
Solvent replacement for green processing (Sherman
et al., 1998);
New applications of supercritical uids (Brennecke,
1996);
Use of supercritical uids for dierent processes including new development (Marr and Gamse, 1990);
Fourth Italian Conference on Supercritical Fluids
and their Applications (1999) (Reverchon, 1999);
High Pressure Engineering, Proceedings in International Meeting of the GVC-Fachausschu Hochdruckverfahrens technik, Karlsruhe, 35 March,
1999 (Polymers, materials, hydrothermal treatment,
reactions, phase equilibria and thermodynamics, natural food processing, particle formation, separation
techniques) (GVC, 1999);
Fifteenth Montreux Symposium on Liquid ChromatographyMass Spectrometry, Supercritical Fluid;

PMMA
PR e.o.s.
PRSV e.o.s.
RK e.o.s.
SAFT
sc
SCWO
SFC
SFE
SPE
SPME
SRK e.o.s.
TD
TDM
VLE
VOC

poly(methyl methacrylate)
PengRobinson equation of state
PengRobinsonStryjekVera e.o.s
RedlichKwong equation of state
statistical associating uid theory
supercritical
supercritical water oxidation
supercritical uid chromatography
supercritical uid extraction
solid-phase extraction
solid phase micro-extraction
SoaveRedlichKwong equation of
state
tracer diusion
Taylor dispersion method
vaporliquid equilibrium (equilibria)
volatile organic compounds

ChromatographyMass Spectrometry, Capillary

ElectrophoresisMS and Tandem-MS Montreux
(Switzerland), 113 November, 1998 (van der Greef,
1999);
Fourth International Symposium on Supercritical
Fluids, 1114 May, 1997, Sendai, Japan; 1
High Pressure Chemical Engineering (Third International Symposium on High Pressure Chemical Engineering, Z
urich, Switzerland, 79 October, 1996)
(von Rohr and Trepp, 1996).
2.2. Research activities
Green chemistry and green engineering in the US
(Longanecker, 1999);
Supercritical Fluid Research Group at Pacic Northwest National Laboratory (PNNL), Richland, WA,
USA, http://www.pnl.gov/scruid/inex.html 2 (Yonker et al., 1997);
Research activities on supercritical uid science and
technology in Japan A review (coal-tar pitch, thermodynamic properties, intermolecular potential
functions, saturated-liquid densities, phase equilibrium, infrared spectroscopy);
Research activities on supercritical uid (SCF) science and technology (primarily) under the Japanese
government funded; priority research area on supercritical uids.

K. Arai, J. Supercrit. Fluids 13 (1-3) VII (1998). (Special

issue, Selected papers).
2
Presidential (Clinton/Gore) Green Chemistry Challenge
Award for ``Design and Application of Surfactants for Carbon
Dioxide'' (1997).

W.H. Hauthal / Chemosphere 43 (2001) 123135

I Solution Structures. Simulations and spectroscopic

experiments to study the interactions in sc-uids and
clustering dynamics.
II Equilibrium and Transport Properties. Measurement and correlation of properties of refrigerants, triglycerides and fatty acids, alcohols, and coal chemicals.
III Separations and Processing. Exploration of applications of SCF for separating and processing natural
products, biomass, coal and coal liquids, polymers, and
ceramics.
IV Reactions. Research on homogeneous and heterogeneous reactions which include carboxylations,
photo-induced, FischerTropsch synthesis, enzyme
reactions, and material conversions, new processes for
converting waste cellulose and polymers into chemical
intermediates and processes for producing thin lms and
metal oxides are shown to have great promise. (Saito,
1995)
Objectives of the new working group ``Umwelt und
ressourcenschonende Synthesen und Prozesse'' of the
German Chemical Society's (GDCh) FG ``Environmental Chemistry and Ecotoxicology'' as well as
the First Symposium ``Nachhaltigkeit (sustainability) in der Chemie und ihren Produkten'', 2325 August 1999, T
ubingen, Germany (Bayer and Lenoir,
1998).
The contributions of synthesis research on the way to
sutainability (Winterfeldt, 1999).
The search for environmentally friendly processes
(Bolm et al., 1999).
Deutsche Forschungsgemeinschaft (DFG): Priority program ``Supercritical uids as solvents
and reaction media'' (Increases of reaction rates, ammonolysis, amination, degradation of pollutants,
homogeneous catalysis, enzymatic catalysis, and
others).
3. Fundamentals
3.1. Supercritical uidsgeneral
The physical state of supercritical uids (structure,
hydrothermal reactions, liquid water, 1000 bar, spectroscopy) (Gorbaty and Bondarenko, 1998);
Supercritical water. The properties and applications
to chemical reactions as a medium (Ikushima, 1998);
Supercritical Water (Franck and Weing
artner, 1999);
Hydrogen-bonding in light and heavy water under
normal and extreme conditions (water model, MD,
MC simulations, central-force model, vapor coexistence curve, polarizable water) (Guillot and Guissani,
1998);
High-pressure investigations of uid mixtures Review and recent results (critical phenomena supercritical gases Spectroscopy) (Schneider, 1998a).

125

(1) Fluiduid and soliduid phase equilibria including the critical behavior of binary mixtures,
(2) Liquidliquid phase separations at very high
pressures up to about 3 GPa in a diamond anvil cell,
(3) The high-pressure phase behavior of ternary systems exhibiting cosolvency and miscibility windows,
(4) The solubilities of dyestus in supercritical solvents by static or ow methods,
(5) The determination of binary diusion coecients
of low-volatile substances in supercritical solvents such
as CO2 by a dynamic method,
(6) Solvatochromism under pressure as a measure of
solutesolvent interactions.
3.2. Fluid phase equilibria phenomenology
General:
Phase equilibrium investigations of uid systems at
high pressures (Schneider, 1993),
High pressure investigations on uid system A challenge to experiment, theory and application (Schneider, 1991).
Phenomena:
Barotropy (Pohler et al., 1996),
The building-up of phase diagrams (Calado and Canongia Lopes, 1999),
Closed-loop liquidliquid immiscibility (binary-uid
mixtures, phase-behavior, 2-component solutions,
microscopic eects, directional attractive forces,
weak interacting isotropic uids) (Yelash and Kraska, 1999a),
Closed-loop critical curves (2-component solutions,
phase-diagrams, mixtures) (Yelash and Kraska,
1999a; Yelash et al., 1999),
Cosolvency eect and miscibility windows (binary
and ternary mixtures of supercritical CO2 with tetradecanoic acid and docosane up to 43 MPa and 393 K
(Pohler and Schneider, 1995), . . .of sc-CO2 with a
1-alkanol and an n-alkane up to 100 MPa and 393
K (Pitla et al., 1998),
Co-volume eects on the closed-loop liquid-liquid
immiscibility in binary uid (cross co-volume, double
critical end point (DCEP) line, critical pressure step
point (CPSP) line, critical pressure at point (CPFP)
(Yelash and Kraska, 1999b),
Enhancement factors of solids in supercritical gases
(empirical evaluation method) (Vetere, 1998),
Fluid opacity (application for determining the phase
behavior of binary mixtures near the critical loci
CO2 plus ethane and CO2 plus propane (Martin
et al., 1999),
Global phase behavior/diagram (Yelash and Kraska,
1999a; Yelash et al., 1999),
Inuence of a generalized attraction term of an equation of state on the phase behaviour (Yelash et al.,
1999);

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W.H. Hauthal / Chemosphere 43 (2001) 123135

Liquidliquid immiscibility (vapourliquid-, liquid

liquid-equilibria, 2-component solutions, alkanes)
(Yelash et al., 1999);
Modier eects in supercritical CO2 extraction from
various solid matrices (analyte/matrix interaction,
analyte/modier/matrix complex, solvatochromic parameters, solvent modication, environmental samples (Jeong and Chesney, 1999);
Patterns of soliduid phase equilibria: New possibilities? (Garcia and Luks, 1999);
Unusual chemical thermodynamics (Sandler, 1999b).
Structural investigations and reactions:
Are there hydrogen bonds in supercritical water?
(proton NMR chemical shift for water (25600C,
1400 bar), large changes in chemical shift (4.1
ppm) through changes in the hydrogen bond network; there are still 29% as many hydrogen bonds
at 400C and 400 bar as for room temperature water,
thermodynamic properties, computer-simulation)
(Homann and Conradi, 1997a).
Hydrogen bonds in supercritical methanol and ethanol? (chemical shift measurements of the hydroxyl
protons in methanol and ethanol up to 450C and
over a wide range of pressures, MD simulation,
NMR, density, diraction, mixtures, alcohols) (Homann and Conradi, 1998b).
Hydrogen exchange reactions in supercritical media
monitored by in situ NMR (hydrogen exchange rate
can be adjusted by changing pressure (density) at a constant sc-temperature, deuteration reactions, high-temperature high-pressure NMR, supercritical methanol,
ethanol and water) (Homann and Conradi, 1998a).
Acceleration of synthetic organic reactions using supercritical water: noncatalytic Beckmann and pinacol
rearrangements (great increase in the local proton
concentration around the organic reactants, homogeneous catalysis, oxidation, high-pressure and
high-temperature FTIR, Raman-spectroscopy, cyclohexanone-oxime, liquid and superheated water, CO2 )
(Ikushima et al., 2000).
Raman spectroscopy study on the dynamic behavior
of nitrate anion in zinc nitrate solution at high temperatures and pressure (supercritical water oxidation,
hydration, MD, light-scattering, aqueous-solutions,
hydrothermal solutions, electrolyte-solutions, carbonate anions) (Ikushima and Arai, 1998).
Raman spectral studies of aqueous zinc nitrate solution at high temperatures and at a high pressure of
30 Mpa (direct measurement of dynamic behavior
of ions in an aqueous solution at high temperatures
and pressure using Raman spectroscopy, ion-solvent
interactions, relaxation, perpendicular diusion constant, slightly damped free-rotor (SDFR) model, oxidation, hydration, MD, simulation, supercritical
water, hydrothermal solutions, electrolyte-solutions)
(Ikushima et al., 1998).

Micropolarity of sodium bis(2-ethylhexyl) sulfosuccinate reverse micelles prepared in supercritical ethane

and near-critical propane (E-t(30) values, microemulsion phases, AOT reverse micelles, spectroscopy,
supercritical ethane, near-critical propane, 2,6-diphenyl-4-(2,4,6-triphenylpyridinio)-phenolate,
water)
(Shervani and Ikushima, 1999).
In situ spectroscopy of polymers subjected to supercritical CO2 plasticization and dye impregnation
(PMMA segmental mobility, poly(methyl methacrylate) lms, impregnate disperse Red 1 dye polymer
lm, enhanced diusion process, hydrogen bonding,
Ft-ir, UV/Vis) (Kazarian et al., 1997).
3.3. High-pressure phase equilibria solubilities
General:
Phase equilibrium data needs for the design of supercritical uid extraction columns (Nunes da Ponte
et al., 1999);
Critical temperatures, pressures, and densities for the
mixtures CO2 C3 H8 , CO2 nC4 H10 , C2 H6 C3 H8 , and
C3 H8 nC4 H10 method of calculation) (Vanpoolen
and Holcomb, 1999);
Ternary phase equilibria for the NaClNa2 SO4 H2 O
system at 200 and 250 bar up to 400C (solubility data, hydrothermal, ternary, vaporliquid and solid
uid equilibria, liquidvapor relations, NaClH2 O,
300500C) (Dipippo et al., 1999);
Predicting the approximate solubilities of (hydrocarbon) solids in dense CO2 (Trabelsi et al., 1999);
Environmental Pollution (Sandler, 1999a).
Solubility of:
behenic acid in supercritical carbon dioxide with npentane or n-octane cosolvents (Guan et al., 1999);
behenic acid and ethylbehenate in sc-CO2 (fatty acids, immobilized lipase, stearic-acid, triolein) (Nakaya et al., 1999);
chelating agents and metal-containing compounds in
supercritical uid CO2 (Review) (Smart et al.,1997);
anthraquinone dyes in sc-CO2 investigations by a
ow method (Wagner et al., 1999a);
disperse and Mordant dyes in supercritical CO2 (Guzel and Akgerman, 1999);
disperse dyes in supercritical CO2 (Ozcan et al., 1997;
Tusek and Golob, 1999);
dyestus in near- and supercritical uids up to
180 MPa (1,4-bis-(n-alkyl-amino)-9,10-anthraquinone
dyestus, soliduid phase equilibria, UV/VISspectroscopy, beta-carotene, CO2 , nitrous oxide,
critical region, all-trans) (Tuma and Schneider, 1999);
PAH in supercritical CO2 (Yamini and Bahramifar,
2000);
PAH in subcritical water from 298 K to 498 K
(PCBs, extraction, chromatography) (Miller et al.,
1998);

W.H. Hauthal / Chemosphere 43 (2001) 123135

PAH (cholesterol, pyrene, chrysene, perylene, benzo[ghi]perylene) in sc-CO2 from 313 to 523 K and
pressures from 100 to 450 bar (Miller et al.,
1996);
chlorinated hydrocarbons in sc-CO2 from 313 to
413 K and at pressures from 150 to 450 bar (PAHs,
CO2 extraction eciencies, environmental samples,
uids, solids, cholesterol) (Miller et al., 1997);
PCB (individual polychlorinated biphenyl congeners
in supercritical uids: CO2 , CO2 /MeOH and CO2 /nC4 H10 ) (Anitescu and Tavlarides, 1999);
TNT and wax and their fractionation from an explosive material using a supercritical uid (Ashrafkhorassani and Taylor, 1999);
veterinary sulfonamides in sc-CO2 by a recirculating
equilibrium method (uid extraction, recovery)
(Hampson et al., 1999).
3.4. Solvatochromism/partition coecients
Solvatochromism in supercritical uids (IR- and UVspectroscopy, solvent polarity parameters, phase-behavior, indicators, basicity, shifts) (Maiwald and
Schneider, 1998);
Solvatochromism in supercritical uids (solvatochromic solubility parameters pi and beta of the pure uids CO2 , N2 O, CClF3 , SF6 , and NH3 ) (Schneider,
1998b);
Solvatochromic study of basic cosolvents in supercritical ethane (Hafner et al., 1997);
Study of interactions in supercritical uids and SFC
by solvatochromic LSER (statistical thermodynamic
treatment, molecular interactions, solvent strength,
correlation of SFC retention data with of solute solvatochromic parameters) (Weckwerth and Carr,
1998);
Interpretation of solubility and solvation of phenol
blue in sc-CO2 based on solute-solvent interaction
evaluated by solvatochromism) (Sasaki et al.,
1999);
Partition coecients of organic substances in twophase mixtures of water and CO2 at pressures of
8 to 30 MPa and temperatures of 313333 K (phase
equilibria, SFE, ternary mixtures, new apparatus,
phenol, benzoic acid, benzyl alcohol, 2-hexanone, vanillin, caeine) (Brudi et al., 1996);
Partition coecients of aromatic organic substances
in two-phase mixtures of water and CO2 at pressures
from 8 to 30 MPa and at temperatures of 313333 K.
Part II (enhancement factor, enthalpy of hydration,
phase equilibria, solubility, solids, CO2 ) (Wagner
et al., 1999b);
Partitioning of solutes and cosolvents between supercritical CO2 and polymer phases (impregnation, dyeing, partition coecient, diusion, Ft-ir, UV/Vis,

127

poly(methyl methacrylate), cross-linked poly(dimethylsiloxane), cosolvents (methanol, acetone))

(Kazarian et al., 1998);
Supercritical CO2 soil partition coecients (PAHs,
chlorobenzenes, equilibrium, SFE) (Gray et al., 1995).
3.5. Systematics, models, equations of state and other
correlations
Global phase diagrams and their applications to uid
mixtures at high pressures (Deiters);
Global phase diagram (Kraska, 1999);
High pressure investigations of uid mixtures Experimental basis of GPD (Schneider, 1999);
Van der Waals-like GPD (Quasi-binary mixtures, liquidliquid immiscibility, tricritical phenomena)
(Scott, 1999);
A classication of phase diagrams of ternary uid
systems (Bluma and Deiters, 1999);
From global phase diagrams to new optimized equations of state (Yelash and Kraska, 1999a);
A three-phase ternary model for CO2 -solidliquid
equilibrium at moderate pressures (CO2 -naphthalene-(toluene, n-pentane), cosolvents, SFE, volatile
matter of mineral coals, PR/Stryjek-Vera e.o.s.)
(Darocha et al., 1996);
General phase behavior in nonionic microemulsion
systems (Burauer et al., 1999);
E.o.s. for aqueous ethanol mixtures (270420 K;
pressures up to 200 MPa) (Takiguchi and Uematsu,
1999);
Prediction of VLE using PengRobinson and Soave
RedlichKwong equation of state (Ghosh, 1999);
Prediction and correlation of triglyceride-solvent solidliquid equilibria with activity coecient models
(theory, excess functions, sc-CO2 , polymer-solutions,
solubility, UNIFAC, acid, fat) (Smith et al., 1998);
Prediction of the critical locus in binary mixtures using e.o.s. I. Cubic e.o.s., classical mixing rules, mixtures of methanealkanes (supercritical equilibria,
phase-behavior, GPD, critical lines, unlike pair parameter (k12 ), calculation method, RK e.o.s., PR
e.o.s., uid mixtures, high pressures, low temperatures) (Polishuk et al., 1999);
Prediction of soliduid equilibria in sc-CO2 using
LSER (activity coecient, enthalpy of fusion, partial
molar volumes, innite dilution, calorimetric measurement, solubility parameters, phase-equilibria,
chromatography, phenanthrene, enthalpies, solvents,
solutesolvent interaction model, liquid- and gas-like
densities) (Bush and Eckert, 1998);
An e.o.s. describing the critical region: extension to
high pressure (liquid vapor equilibria, thermodynamic properties, temperature relation, binary mixtures,
CO2 , uids, cross-over, density) (Leonhard and
Kraska, 1999).

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W.H. Hauthal / Chemosphere 43 (2001) 123135

4. Chemical engineering data

4.1. Diusion coecients/mass transfer
Diusion coecients in supercritical uids: available
data and graphical correlations (acid methylesters,
SFC, molecular-diusion (MDif), tracer diusion
(TD), aromatic-hydrocarbons, n-hexane, naphthalene, binary systems) (Suarez et al., 1998).
Theoretical studies of energetics and diusion of aromatic compounds in sc-CO2 (MD, Lennard-Jones,
ab-initio, benzene dimer, force-eld, hard-sphere,
CO2 dimer, model) (Coelho et al., 2000).
Innite-dilution diusion coecients in supercritical
and high-temperature liquid solvents (calculation
method, SFC, TDM, TD, MDif, organic-compounds, binary systems, benzene, naphthalene) (He,
1998a).
Prediction of binary diusion coecients of solutes in
supercritical solvents (SFC, TD, MDif, transport, organic compounds, benzene, naphthalene, CO2 , acid)
(He, 1997).
Estimation of innite-dilution diusion coecients in
supercritical uids (SFC, TD, Mdif, organic compounds, binary systems, benzene, naphthalene,
CO2 , acid) (He and Yu, 1997).
Mutual diusion coecients of benzene in sc-CO2
(acetone, critical point, TDM, SFC) (Ago and Nishiumi, 1999).
Physical properties and structure of supercritical
water (self-diusion) (Nakahara and Matubayasi,
1999).
Steady-state parallel plate apparatus for measurement of diusion coecient in sc-CO2 (SFC, binary
mixtures, equilibria, acid methyl-esters, naphthalene,
benzene, caeine) (Tuan et al., 1999b).
TD coecients of solutes in supercritical solvents
(method of calculation, SFC, MD, organic compounds, binary systems, benzene, naphthalene, transport, acid) (He et al., 1998).
TD coecients of benzene in dense CO2 , at 313.2 K
and 8.530 MPa (experiment, transport properties,
binary diusivity, benzene, TDM, SFC, esters) (Funazukuri and Nishimoto, 1996).
A kinetic approach for predicting diusivities in
dense uid mixtures (statistical mechanics, mixture,
binary diusion coecients, hard-sphere theory,
TD, self-diusion, transport-properties, aromatic hydrocarbons, liquid cyclohexane, repulsive forces)
(Dariva et al., 1999a).
Dense uid self-diusion coecient calculations using perturbation theory and molecular dynamics
(smooth-sphere theory, hard-sphere theory, repulsive
forces, pressure, temperature) (Coelho et al., 1999).
Binary diusion coecients of low-volatile substances in supercritical solvents (Schneider, 1998a).

Importance of thermal diusion in high subcritical

and supercritical aqueous solutions (electrochemical
cells, high temperature, coecients, electrolytes,
NaNO3 aqueous solutions, forced convection, Lewis
number, Soret coecient) (Lvov et al., 1998).
Prediction of diusion coecients of liquid and solid
solutes in supercritical solvents (SFC, CO2 , TD,
Mdif, organic compounds, binary systems, benzene,
naphthalene, transport, acid) (He, 1998b,c).
Mass transfer in polymers in a sc-CO2 -atmosphere
(diusion of CO2 in poly-(ethylene-terephthalate),
diusion of disperse dyes in PET (strongly depends
on the dye), mass transfer mechanism in the amorphous regions of polymers, membrane separations
of gasuid mixtures, generation of foams, extraction
of impurities, new experimental method to determine
diusion coecients, gravimetric measurements of
mass transport, swelling of polymers in CO2 , glassy
polymers, sorption) (von Schnitzler and Eggers,
1999).
Numerical modeling of mass transfer in the supercritical antisolvent process (counterdiusion model,
droplet swelling, particle formation, two-way mass
transfer, compressed uid antisolvent, droplet vaporization, ne particles, precipitation, powders, crystallization, microspheres, solubilities (Werling and
Debenedetti, 1999).
4.2. Other properties
Measurement and modeling of viscosity of sc CO2 /
biomaterial(S) mixtures (corresponding states, prediction, fatty-acids, oils) (Tuan et al., 1999a);
high-pressure viscosity of polystyrene solutions in
toluene plus CO2 binary mixtures (polymer-solutions, density, miscibility, poly(dimethylsiloxane), antisolvent, temperature) (Yeo et al., 2000);
liquid densities at high pressures (alkanes, alkenes)
(Aalto and Keskinen, 1999);
the density of hydrogen uoride at high pressures to
973 K and 200 MPa (e.o.s., high temperature, sc-uid) (Franck et al., 1999);
partial molar properties from solute retention in
SFC: thermodynamic framework, advantages, and
limitations (dilute near-critical mixtures, partial
molar properties, fugacity coecient, solute retention, temporal column parameters, pressure phaseequilibria, innite dilution, statistical thermodynamics, generalized treatment, critical point) (Roth,
1998);
on the unique behavior of molar excess enthalpies for
the supercritical uid mixtures (MC simulation,
Lennard-Jones mixtures) (Fujihara et al., 1997);
calorimetry in the near-critical and supercritical
regions. Nitrous oxide + hydrocarbon mixtures
(Renuncio et al., 1999);

W.H. Hauthal / Chemosphere 43 (2001) 123135

the Lewis number under supercritical conditions (premixed ames, curvature) (Harstad and Bellan, 1999);
on transport properties of hot liquid and sc-water
and their relationship to the hydrogen bonding; (correlation analysis, diusion coecient, self-diusion,
MD, hydrogen bonding, viscosity, mechanism,
1000C, mechanism) (Marcus, 1999);
heat transfer from sc-carbon dioxide in tube ow: A
critical review (Pitla et al., 1998).
4.3. Corrosion behaviour of construction materials
Corrosion in supercritical water oxidation systems: A
phenomenological analysis (Kriksunov and Macdonald, 1995).
Corrosion behaviour of:
inorganic materials in subcritical and supercritical
aqueous solutions (Kaul et al., 1999);
nickel-base alloy 625 (NiCr22 Mo9 Nb, 2.4856) and
ceria stabilized tetragonal zirconia polycrystal
(Ce-TZP) against oxidizing aqueous solutions of
hydrouoric acid (HF), hydrobromic acid (HBr),
and hydriodic acid (HI) at sub- and supercritical temperatures (Kritzer et al., 1999d);
nickel-base alloy 625 in sub- and supercritical aqueous solutions of HNO3 in the presence of oxygen
(high-temperature, chloride, waste) (Kritzer et al.,
1999b);
nickel-base alloy 625 in sub- and supercritical aqueous solutions of oxygen: a long time study (high-temperature water, chloride) (Kritzer et al., 1999a);
niobium in oxidizing sub- and supercritical aqueous
solutions of HCl and H2 SO4 (Kritzer et al., 1999c);
tantalum in oxidizing sub- and supercritical aqueous
solutions of HCl, H2 SO4 and H3 PO4 (Friedrich et al.,
1999).
5. Chemistry and chemical engineering
5.1. Supercritical uid extraction
General:
SFE (Cliord, 1999);
Selectivity in SFE. Recovery of pesticides from model
matrices (CO2 -methanol, soil, residues) (Berglof et al.,
1999);
Supercritical Fluid Chromatography and Extraction.
[Review] (PAHs, o-line SFE, ASE, light-scattering
detection, chiral stationary-phase, polymethylsiloxane encapsulated particles, enzyme-immunoassay
analysis, benchtop MS, linked immunosorbent assay)
(Chester et al., 1998);
design and analysis of supercritical extraction processes (process optimization, rational use of energy,
solubility) (Gani et al., 1997);

129

Industrial process development:

Countercurrent multistage gas extraction (SFE) processes (supercritical uid (gas) extraction, phase equilibria, height of theoretical stages or transfer units,
hydrodynamics of countercurrent ow, simulation,
packing materials, pressure drop, ooding points,
cost analysis) (Brunner, 1998);
advances in sc-CO2 technologies (uid chromatography, antisolvent, extraction, separation) (Sihvonen
et al., 1999);
design of a SFE process for separating mixtures incurred in enzyme-catalyzed reactions (model system: transesterication of ethyl acetate and
isoamyl alcohol yielding ethanol and isoamyl acetate in sc-CO2 , countercurrent extraction, RK
e.o.s, integrated process scheme) (Chrisochoou and
Schaber, 1996);
energy analysis of sc-CO2 extraction processes (exergy analysis, supercritical extraction cycles) (Smith
et al., 1999).
Environmental:
enhanced catalyst reactivity and separations using
water/CO2 emulsions (hydrogenation, microemulsions, environment) (Jacobson et al., 1999b);
SFE of bioaccumulated mercury from aquatic plants
(solid materials, metal-ions, recovery, pH) (Wang
and Wai, 1996));
supercritical CO2 extraction as a clean degreasing
process in the leather industry (fat, recovery, sheepskins, disperse dyes, bers) (Marsal et al., 2000);
supercritical CO2 extraction of soil-water slurries
(PAH, phenolics, soil extraction, gas extraction, organics, model prediction for a three-phase system using two-phase partitioning data, octanol-water
partitioning correlation for soil-water partition coefcients) (Green and Akgerman, 1996);
inuence of water on the SFE of naphthalene from
soil (innovative soil remediation technology, partition coecient, mass transfer coecient, pollutants,
matrices, sorption, water content below 10%) (Smyth
et al., 1999)
soil component interactions with 2,4-dichlorophenoxyacetic acid under supercritical uid conditions
(sc-CO2 modied with benzoic acid/methanol, selected model soil components, adsorption to mineral surfaces, diusionlimited release from porous materials,
pH-dependent partitioning between solid and sc-uid
phases, derivatization, pesticides, herbicides, gibbsite,
goethite, illite, silica gels, humic acid, sodium humate) (Rochette et al., 1996);
removal of polychlorodibenzodioxin and dibenzofuran from y ash (Gabarra et al., 1999);
chlorouoroalkanes from rigid polyurethane foams
(polymer recycling) (Filardo et al., 1996);
petroleum hydrocarbons from soil by mechanical
shaking (PAH) (Schwab et al., 1999);

130

W.H. Hauthal / Chemosphere 43 (2001) 123135

oil contaminant removal from drill cuttings by supercritical extraction (HFC-134a and propane as the extractive solvents, reduction of oil-based mud
contamination of drill cuttings to a level allowing oshore disposal, possible use of oil-based mud in environmentally sensitive areas as a major benet for
drilling operations, commercial process design and
cost estimate) (Eldridge, 1996);
recovery of s-triazine herbicides and associated
breakdown products from granular activated carbon
using SFE (CO2 /acetone, activated carbon, ow rate,
recovery, degradation, pesticides, adsorption, eciency, pollutants, atrazine, simazine, deethylatrazine, diethylsimazine) (Robertson and Lester, 1995);
chemical recycling of phenol resin by supercritical
methanol (terephthalic acid, poly(ethylene-terephthalate), polyethylene, decomposition, degradation)
(Ozaki et al., 2000).
5.2. Chemical syntheses and reactions
General:
Chemical synthesis using supercritical uids (supercritical uids as media for chemical reactions
(motivation for use of SCFs in modern chemical
synthesis), Phase Behavior and Solubility, physical
properties as related to chemical reactions, experimental techniques (high pressure reaction equipment design, ectraction and related separation
techniques, precipitation and crystallization techniques, microemulsions, emulsions and latexes),
spectroscopy of solutions (vibrational spectroscopy, NMR spectroscopy, UV, EPRS, X-ray and related spectroscopic techniques), reactions in SCF
(synthesis of inorganic solids, synthesis of coordination compounds, Stochiometric organic reactions, photochemical and photoinduced reactions,
polymerizations in dense CO2 , free-radical polymerization in reactive SCFs, metal-complex catalyzed reactions, heterogeneous catalysis, enzymatic
catalysis, phase transfer and ammonium salt catalyzed reactions) [Monograph] (Jessop and Leitner,
1999b).
Chemical reactions in supercritical uids [review] (scCO2 and water as reaction media, homogeneous catalysis, increased rates and selectivities because of
high solubility of reactant gases, rapid diusion between phases, weaker solvation of the catalyst, transition metal complex, DielsAlder reaction, Tropsch
synthesis reaction, organometallic photochemistry)
(Ikariya et al., 1995).
Chemistry in supercritical water (Br
oll et al., 1999).
Organic chemical reactions in supercritical water
[review] (pressure aqueous environments, hightemperature chemistry, near-critical water, Ramanspectroscopic measurement, continuum electrostatics

model, acidbase behavior, hydrothermal reactions,

phenol oxidation, S(n)2 reaction) (Savage, 1999).
Investigating the synthesis potential in supercritical
water (Krammer et al., 1999).
Chemical synthesis in supercritical carbon dioxide.
``The Better Solution?'' ``Supercritical CO2 is an environmentally benign solvent for chemical synthesis
with homogeneous transition metal catatalysts. The
unique properties of this medium allow ecient catalyst recycling and can lead to increased activities
and selectivities. The design of CO2 -soluble catalysts
is of particular importance for the application of this
novel solvent'' (Leitner, 2000).
Solvation in supercritical uids: its eects on
energy transfer and chemical reactions [review]
(charge-transfer-state, liquid transition region, Xray-scattering, rotational friction coecients, diusion-controlled reactions, electron-transfer reactions,
pyrene excimer formation, highly excited azulene,
free-space model) (Kajimoto, 1999).
Solvent density inhomogeneities in supercritical
uids [review] (LennardJones uid, continuum
electrostatics model, MD simulation, compressible
dielectric uid, solute-solute correlations, transferstate formation, reaction-rate constants, MC simulation, highly excited azulene, charged hardsphere)
(Tucker, 1999).
Thermodynamic studies of chemical equilibrium in
sc-CO2 /cosolvent solutions using UV-Vis spectroscopy preferential clustering, tautomeric equilibrium,
benzophenone, ethane) (Lu et al., 1999).
Syntheses/reactions:
Supercritical water oxidation: state of the art
(Schmieder and Abeln, 1999);
Oxidation of hydrogen and carbon monoxide in suband supercritical water reaction kinetics, pathways,
and water-density eects, (1) Experimental results
(sensitivity analysis, oxygen mixtures) (Holgate and
Tester, 1994b), (2) Elementary reaction modeling
(OH + CO, rate-constant, temperature dependence,
pressure-dependence, self-reaction, gas-phase, HO2 ,
mechanism, combustion) (Holgate and Tester,
1994a);
Kinetics and mechanism of methane oxidation in supercritical water (modelling, combustion chemistry,
hydrogen) (Savage et al., 1998);
Separation and destruction of environmental pollutants by oxidation in CO2 (Dahmen and Dinjus,
1999);
Hydrolysis and oxidation in subcritical and supercritical water: connecting process engineering science to
molecular interactions (waste treatment, methanol
oxidation, fundamental kinetics, ion solvation, abinitio, transport-properties, neutron-diraction, spectroscopic measurement, hydrogen) (Tester and Cline,
1999);

W.H. Hauthal / Chemosphere 43 (2001) 123135

Hydrolysis of esters in subcritical and supercritical

water (kinetics, mechanism, ion-product, oxidation,
conversion, methanol, acid) (Krammer and Vogel,
2000);
Kinetic study of hydrolysis of methylene chloride
from 100C to 500C (sc-water, rate constants, oxidation, groundwater) (Salvatierra et al., 1999);
Incorporation of parametric uncertainty into complex kinetic mechanisms: Application to hydrogen
oxidation in supercritical water (fundamental kinetics, diusion, CO, methanol) (Phenix et al., 1998);
Hydrothermal oxidation of model molecules and industrial wastes (SCWO, methanol) (Cansell et al.,
1998);
Rate of dibenzyl ether decomposition in supercritical
water (decomposition kinetics, hydrogen transfer-reactions, coal, pyrolysis, kinetics) (Funazukuri et al.,
1997);
Catalytic hydrodesulfurization of dibenzothiophene
through partial oxidation and a water-gas shift reaction in sc-water (Tropsch synthesis reaction, coal-tar
pitch, uid, extraction) (Adschiri et al., 1998);
Homogeneous organic reactions as mechanistic
probes in supercritical uids [review] (solvation ultrafast dynamics, laser ash-photolysis, Diels-Alder reaction, solvent-density dependence, transfer-state
formation, highly excited azulene, continuum electrostatics model, diusion-controlled reactions, freeradical polymerization, time-resolved uorescence)
(Brennecke and Chateauneuf, 1999);
Highly regio- and enantio-selective rhodium-catalysed asymmetric hydroformylation without organic
solvents (sc-CO2 , phosphine-phosphite ligands, enantioselective hydroformylation, homogeneous catalysis, hydrogenation, complexes, olens, propylene,
peruoroalkyl-substituted ligand (R,S)-3-(HF6)-F-2BINAPHOS, substitution pattern of the ligand)
(Francio and Leitner, 1999);
Supercritical uids in heterogeneous catalysis [review] (FischerTropsch synthesis, near-critical conditions, Pt/c-Al2 O3 catalyst, homogeneous catalysis,
selective synthesis, reaction volumes, recycle reactor)
(Baiker, 1999);
The continuous acid-catalyzed dehydration of alcohols in supercritical uids: a new approach to the
cleaner synthesis of acetals, ketals, and ethers with
high selectivity (Compressed liquid water, tert-butyl
alcohol, Naon-h catalyst, heterogeneous catalysis,
1-propanol dehydration, organic-reactions, solid superacids, CO2 , cyclic ethers) (Gray et al., 1999);
Ammonolysis with supercritical NH3 (amine, kinetics, sc-reaction) (Wang et al., 1999);
Synthesis of 1,4-diaminocyclohexane in supercritical
ammonia (amination, cobalt-iron, catalytic amines,
alcohols, transformation, diols) (Fischer et al.,
1999a);

131

Cobalt-catalyzed amination of 1,3-propanediol: effects of catalyst promotion and use of supercritical

ammonia as solvent and reactant (1,3-diaminopropane, 1,3-propanediol, eect of iron and lanthanum
promotion, aliphatic amines, copper, alcohols, methylamines, adsorption, nickel, XPS) (Fischer et al.,
1999b);
Supercritical uids as media for chemical and biochemical reactions (Ikushima and Arai, 1998);
Supercritical uids an interesting medium for chemical and biochemical processes (FTIR study on the
structures of reverse microemulsions in supercritical
ethane, ester synthesis catalyzed by a lipase in CO2 ,
inverted micelles, reversed micelles, aerosol, angle
neutron-scattering, interfacial activation, near-critical region, candida-rugosa lipase, OT) (Ikushima,
1997);
Eect of Pressure on an enzymatic reaction in a supercritical uid (Erickson et al., 1990);
Enzyme catalyzed reactions in dense gases (enzymes,
esterication, high pressure, mass transfer, mucormiehei lipase, oleic-acid esters, n-butyl oleate, immobilized lipase, organic-solvents, esterication, transesterication, pressure, uids) (Knez et al., 1998);
Polymerizations in supercritical CO2 [review]
(compressed uid diluents, consistent-eld-theory,
dispersion polymerization, methyl-methacrylate,
microcellular materials, emulsion stabilization,
metathesis catalysts, elevated pressures, glass transitions, olen metathesis) (Kendall et al., 1999);
Electrochemistry in near-critical and supercritical uids. 9. Improved apparatus for water systems (23
385C) the oxidation of hydroquinone and iodide
(Liu et al., 1997);
Electroorganic synthesis using supercritical CO2 (Reactive-metal anode, electrochemical carboxylation,
sacricial anodes, acids, bromides, voltammetry)
(Tokuda, 1999);
Novel synthesis methods for new materials in solid
state chemistry (borohydrides, electrochemical oxidation reduction, intercalation deintercalation, mechanical alloying, nanoparticles, nitrogen dioxide,
soft chemistry, electrochemical oxidation, structural
relationships, oxides, La2 CuO4 , lithium, temperature,
reduction) (Etourneau, 1999);
Remarkable pressure-dependent changes in diastereoselectivity in supercritical carbon dioxide (Anon.,
1999);
Carbon dioxide and metal centres: from reactions inspired by nature to reactions in compressed CO2 as
solvent [review] (CO2 activation, carbamato metal
complexes, enzyme models, semiconductor photo-catalysis, homogeneous catalysis, copper-catalyzed oxidation, CO2 -soluble chelating-agents, light induced
photoxation, CO2 reduction, transition-metals, active-sites) (Walther et al., 1999);

132

W.H. Hauthal / Chemosphere 43 (2001) 123135

Laser-induced oxidation reactions of ethane in scCO2 (KrF excimer laser, photo-induced oxidation,
Herzberg photoabsorption, oxygen, recombination,
resonance, uids, gases, O2 ) (Otomo et al., 1999);
5.3. Supercritical uid (materials)processing
Processing with supercritical solvents (Mcclain,
2000);
Cleaning of metal parts and components by compressed CO2 (Dahmen et al.);
Dyeing to be clean: use supercritical carbon dioxide
(high-pressure investigations, solubility, impregnation, extraction, bers, lms, spectroscopy, polymers,
azo-dyes) (Kazarian et al., 1999a);
Supercritical uid dyeing of PMMA lms with azodyes (transition, diusion of azo-dyes in a CO2 -swollen matrix of PMMA, tuning by changing the system
pressure, dye partitioning, dye solubility, 180 Mpa, in
situ UV-visible spectroscopy, polymers, methacrylate) (West et al., 1998);
Dyeing of poly-olen bers in supercritical carbon dioxide part 2. Inuence of the dye structure on the dyeing result and fastness properties (Bach et al., 1998a);
Dyeing of synthetic bers in supercritical carbon dioxide (Bach et al., 1998b);
Experience with the UHDE CO2 -dyeing plant on a
technical scale. Part II: concepts for the development
of the pilot plant in respect of a scaling up of the machine (Bach et al., 1999a);
Correlation of solubility data of azo disperse dyes
with the dye uptake of poly(ethylene terephthalate)
bers (PETP) in supercritical carbon dioxide (Bach
et al., 1999b);
Applications of vibrational spectroscopy to characterize poly(ethylene terephthalate) processed with supercritical CO2 (solvent-free processes for advanced
processing of packaging materials and supercritical
uid dyeing of textiles, increased degree of crystallinity, supercritical dyeing of PET samples with azo
dyes, crystallization, morphology and structure, surface orientation, plasticization, impregnation, bers,
lms, FTIR, Ft-raman) (Kazarian et al., 1999b);
Recycling of oil-contaminated grinding sludge (Dahmen and Dinjus, 1999);
Supercritical CO2 processing for submicron imaging
of uouropolymers (hexauoropropylene, inorganic
substrate; silicone polymers; phase-behavior; solubility; copolymers; photoresist; architecture; adhesion)
(Sundararajan et al., 2000).
6. Conclusions
Although not complete, the tables include a large
amount of actual aspects, terms and references (in-

cluding many reviews about both general and more

special topics), which possibly may be helpful in getting
further informations about certain topics from the cited
original literature. The sources are from dierent disciplines of science, e.g., organic, analytical chemistry,
physical chemistry/chemical physics, chemical and other
elds of engineering, environmental, material sciences,
and many others.
Synergies of using supercritical uids and microemulsions as well as additional aspects of supercritical
uids (materials) processing, however, may be subject of
another paper.

Acknowledgements
Financial support from the Fonds der Chemischen
Industrie FCI im Verband der Chemischen Industrie
e.V., Frankfurt am Main, is gratefully acknowledged.

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