The Journal of Supercritical Fluids, 1990,3,51-65 51

Observations on the Solubility of Surfactants and

Related Molecules in Carbon Dioxide at 50 OC
Keith A. Consani’y* and Richard D. Smith*

Chemical Methods and Separations Group, Battelle, Pacific Northwest Laboratories,

Richland, WA 99352

Received January 22, 1990; accepted in revised form May 8, 1990

Qualitative observations regarding the solubility of over 130 surfactants and related molecules in car-
bon dioxide at 50 “C and pressuresof -100-500 bar are presented. The solubility properties of some sur-
factant classes are discussed. Related comments on the behavior of the surfactant/carbon dioxide systems
when water is added, regarding the possibility of microemulsion formation, are also presented.
Keywords: carbon dioxide, surfactants, solubility, microemulsions

INTRODUCTION
The solubility of materials in supercritical carbon
dioxide, which in the past has been the domain either of
petroleum engineers or of curious scientists, has received
increasing attention in the last decade. This growing in-
terest has been primarily due to the beneficial properties
of carbon dioxide; specifically, it is a processing fluid
having a low cost and a relatively benign chemical nature.
Recent experimentation has attempted to identify sur-
factants capable of forming water-in-oil (w/o) microemul-
sions in supercritical carbon dioxide. As a by-product of
that research, extensive qualitative information was ob-
tained regarding the solubility of a large number of surfac-
tant-type molecules in carbon dioxide. Since the experi-
mentation was not designed to yield quantitative informa-
tion, only qualitative observations can be conveyed. We
believe, however, that in the absence of quantitative ther-
modynamic solubilization data for surfactants in carbon
dioxide, such information may be useful to various indi-
viduals using carbon dioxide for enhanced oil recovery
(EOR), supercritical fluid chromatography (SFC), engi-
neering, or extraction technology. General observations
on the qualitative solubility of compounds in carbon diox-
ide may be found in references l-6 and an introduction to
models for solubility in supercritical fluids in references
7-8.
tCurrent address: EG&G Rocky Flats, Inc., Rocky Flats Plant,
P.O. BOX 464, Golden, CO 80402-0464.
EXPERIMENTAL
Materials. The chemicals were obtained directly from
the manufactureror from an SU-500 Chem Services Inc.
(West Chester, PA) surfactant kit. Information regarding
the source of specific materials is listed in Table I. All
chemicals were of recent manufacture, except for the
Chem Services materials (marked CS in Table I), which
were obtained from a Chem Services kit. Carbon dioxide
was Scott Specialty (SFC grade). The solid or pure liquid
commercial surfactants were generally used as received,
without efforts to dehydrate them further. When the sur-
factants were known to be solutions, efforts were made to
remove volatile cosurfactants (alcohols, water, etc.).
Solutions which did not concentrate quickly by evapora-
tion at 40 “C and 1 atm were rotoevaporated or dried by
azeotropic distillation with an appropriate solvent (e.g.,
ether or pentane). Eventually, most were then dried by
vacuum. Sometimes residual involatile liquid solvents
were removed by filtration and washing. For example,
GAF CD-128 (once studied for use in EOR work)9+‘0 was
purified of a significant amount of liquid polyglycol
(remaining from manufacture) by “air-drying” to remove
ethanol and water, filtration to remove the relatively in-
volatile polyglycol, and washing the filtrate with pentane
(in which the fine powder CD-128 was insoluble). In
general, however, beyond drying the surfactants of sol-
vents, we attempted no purification for fear of changing
the composition of surfactants which were mixtures.
52 Consani and Smith The Journdl of Supercritical Fluids, Vol. 3, No, 2, 1990

TABLE I
Qualitative Solubilities of Materials in Carbon Dioxide at 50 “C

Chemical Identification Source & Trade Name Observations

Acids
decanoic acid Aldrich misc. 169 bar
myristic acid cs misc. 269 bar
oleic acid Aldrich misc. 377 bar
perfluorobutyric acid PCR misc. 86 bar, #
perfluorooctanoic acid PCR (>80% straight chain) misc. 97 bar. #

P
~CH,GH,),,--C
I Hampshire (Hamposyl L) and CS sl. sol. liquid, 169 bar and part.? 476 bar
N -CH,COOH
I
CH3

i
IT-coco- N Henkel (Deriphat 15 1C) insol. waxy solid to 388 bar, ##
I
CH,CH,COOH

i
n-coca - N cs sl. sol. waxy solid 278 bar, ##
I
CH,CH,CH,COOH

cF3(cF,WWWO,H Atochem (Forafac 1033) Misc. 144 bar (-#) (solid, liquid)
dodecylbenzene sulfonic acid Continental (CONCO AAS-98S, sl. sol. liquid 130-487 bar
with -1% H2SO4 impurity)
F(CF,CF,),CH,CH,P(O)(OH)2 DuPont (Zonyl UR) part. to nearly misc. 114-585 bar
[F(CF,CF,),CHzCH,Ol,po(oH) dusty fog, some material floats
(waxy solid, liquid)
[CH,(CH,),CH(CZH,)CH,~I~P(O)OH Fluka part. liquid 278 bar

Salts of Acids (Anionics)

sodium perfluorooctanate Battelle prep sl. sol. powder.169-388 bar
(~80% Strt chain)
lithium perfluorooctanate Battelle prep sl. sol. 169-487 bar, swells?, *
(>80% Strt chain)
ammonium perfluorooctanate Fluka insol. powder to 377 bar
sodium decanoate Battelle prep/Aldrich insol. powder to 432 bar
ammonium myristate Battelle prep/Aldrich sl. sol..powder 169-563 bar, swells
aluminum palmitate cs insol. powder to 377 bar, *
lithium stearate Battelle Prep./Aldrich insol. 433 bar, swells 169-579 bar
cobalt stearate cs insol. powder to 377 bar, hazy CO2
lead naphthenate cs insol. to 388 bar
(hard waxy solid, vise. liquid)
nickel oleate CS (dried, but free of acid?) sl. sol. very vise. liquid 388-567 bar
Sn(2-ethylhexanoate)z + diisononyl Witco (Fomrez C-6N) part. 169 bar (DINP presumably)
phthalate

i
C11'+13C

I Grace (Hamposyl L-95) insol. powder to 377 bar, swells?

N-CH,COONa
I
CH3
The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990 Solubility of Sutfactants and Related Molecules 53

Chemical Identification Source & Trade Name Observations

(continued)

cocoy
I
N- CH,COONa Grace (Hamposyl C-30) insol. powder to 390 bar
I
CH3
n-c ,,H2,-N+CH2CH@GNa)2 Henkel (Derihat 160) insol. powder to 388 bar, *
tallow-N-(CH$HQGNa)2 Henkel (Deriphat 154) insol. powder to 388 bar, ##

mC,,H,,--N -CH,CH,COOH
I Henkel (Deriphat 16OC) insol. to 388 bar, swells, * (powder, fluff)
CH,CH,COONa

C,F,,SO,N-CH,COOK
I 3M FC-128 (fluorochain -80% straight) sl. sol. Fine powder, swells, *
W’5
CH3(CH&$H2S0~Na l Hz0 Fluka insol. crystals to 388 bar
calcium dodecylbenzene sulfonate Continental (Conco AAS-75s) insol. powder to 388 bar
potassium perfluoroethyl 3M (FC-98) insol. to 377 bar
cyclohexanesulfonate
potassium perfluoro 3M (FC-95) insol. powder to 317 bar
1-octanesulfonate
n-CsFt7S03Li Battelle prep (from 3M FX-8) sl. sol. (to part?) 169-591 bar
(slightly waxy powder, powder)
F(CF2CF2)&H2CH2SG3X DuPont (TBS) solvent free? part. 169-278 bar
(X = H+ and NI&+) (wax, powder)
(cocoyl)-CH$H$S03Na GAF (Igepon AC-78) insol. powder to 388 bar

P
CH@-M,, -C-N-CH,CH,SO,Na cs insol. powder to 377 bar
I
C”3
C&I&H(C2Hs)CH+04Na Niacet (NAS 08) insol. wax to 585 bar
sodium petroleum sulfates (MW 340-360) CS (purity?) sl. sol. vise. liquid 169-377 bar
butanedioic acid, sulfo-, 1- (2-[( 12- Scher (Schercoquat RMS Na) sl. sol. 169-388 bar
hydroxy- 1-oxo-9-octadecenyl)amino] (waxy powder, powder)
ethyl) ester, disodium salt
butanedioic acid, sulfo-, mono (2- Scher (Schercopol OMS-Na) sl. sol. powder 169-388 bar
[( 1-oxo-9-octadecenyl)amino]ethyl)
ester, disodium salt

Related but Partially Unknown Materials

perfluorosulfonic acid salt Atochem (Forafac 1176) insol. powder to 388 bar
perfluorosulfonic acid salt Atochem (Forafac 1185) sl. sol. powder 278-377 bar
perfluorocarboxylic acid (Cs) salt Atochem (Forafac 1119) sl. sol. powder 169-388 bar
perfluoroalkyl carboxylic anionic ICI (Atsurf F- 13) insol. to 281 bar
(powder, paste)

Polyoxylated Materials
polyoxyethylene 4-lauryl ether Sigma (Brij 30) misc. 388 bar
polyoxyethylene 9-lauryl ether Sigma (Polidocanol) part. liquid 213-311 bar
PEG 400 monolaurate (n-9) CS nearly misc. liquid 377 bar
PEG 600 monolaurate (n- 14) CS part. 377 bar
Polyoxyethylene 23-lauryl ether Aldrich (Brij 35) sl. sol. to part. wax 386 bar
Polyoxyethylene 3-(Ct t-14-iso-, GAF (Emulphogene BC-420) misc. 257 bar, (-#)
Ct3 rich) alkyl ether
polyoxyethylene 2-cetyl ether Sigma (Brij 52) misc. 304-432 bar
(wax, liquid, dissolution)
PEG 300 monooleate (n-7) CS part. liquid 278-377 bar
PEG 6000 monostearate (n-140) cs sl. sol. 160-377 bar (solid, liquid)
polyoxyethylene 25-castor oil Hodag (GR-25) sl. sol. liquid (to part?) 169-377 bar
54 Consani and Smith The Journal of Supercritical Fluids, Vol. 3, No, 2, 1990

Chemical Identification Source & Trade Name Observations

(continued)

polyoxyethylene 4-nonyl phenol cs misc. 388 bar

polyoxyethylene 6-nonyl phenol cs misc. 388 bar
polyoxyethylene 9-nonyl phenol Sigma (Tergitol NP-10) sl. sol. 169 bar, part. 269-487 bar
polyoxyethylene 12-tert. dodecyl cs sl. sol. 180 bar, part. liquid 384 bar
mercaptan
(2-tert-dodecyl mercaptoethanol) (CS) (misc. 169-377 bar)

Related but Partially Unknown Material

F(CF,CF,),~H,CH~20)~ DuPont (Zonyl FSN-100) nearly misc. paste/liquid 377 bar

same as above, with different y DuPont (Zonyl FSO-100) nearly misc. 377 bar
for FSN & FSO, y = 10-15
ethoxylated polyfluoroalcohol Atochem (Forafac 1110) part. to nearly misc. liquid 377 bar
fluoroaliphatic (C4 to C7) 3M (partially dried) part. liquid 169432 bar
oxyethylene adduct (87%) (FC 170-C)
polyoxyethylene glycols (13%)
fluorinated alkyl ethers 3M (FC-740, with naphtha part. 213-377 bar (Tacky solid, liquid)
plus naphtha (C&t t) 50%/50% partially evaporated)

Hydroxy compounds
sorbitan monolaurate Fluka (Span 20) sl. sol to part. liquid 377 bar
sorbitan trioleate Fluka (Span 80) sl. sol. 377 bar (wax, liquid)
sorbitan monostearate Fluka (Span 60) sl. sol.? 377 bar
glyceryl monolaurate cs sl. sol. 169 bar, part. liquid 377 bar
glyceryl monostearate cs misc. 388 bar (waxy flakes, liquid)
glyceryl dilaurate cs nearly misc. liquid 377 bar

Quaternary Ammonium Salts

dodecyl trimethyl ammonium iodide Battelle prep. (from Kodac insol. powder to 388 bar
bromide)
tetradecyl trimethyl Fluka insol. powder to 388 bar, *
ammonium bromide
cetyl trimethyl ammonium bromide cs insol. powder to 377 bar
tetraoctyl ammonium bromide Aldrich sl. sol. 278-388 bar
dimethyl dicoco ammonium chloride Akzo (Arquad 2C-75) sl. sol. 388487 bar, floats
(wax, liquid)
dimethyl dicoco ammonium Akzo (Arquad 2C-nitrite) sl. sol. 278-388 bar
nitrite 86% (wax, liquid)
chloride 14%
(diisobutylcresoxyethoxyethyl) cs insol. powder to 377 bar
dimethyl benzyl ammonium chloride
(N(C,H,),(CH,)[CH2CH2~C,CH,oo7Hl)+Cl- Witco (Emcol CC-9) sl. sol. liquid 278 bar
(N(C,H,),(CH,)[CH,CH,oo40H1)+Cl- Witco (Emcol CC-42) sl. sol. liquid 169487 bar
polypropoxy quaternary Witco (Emcol CC-57) sl. sol. vise. liquid 388 bar
ammonium phosphate
stearamidopropyl dimethyl cs sl. sol. powder 278-377 bar
Phydroxyethyl ammonium phosphate
morpholinium myristate Battelle prep. (Aldrich/ part. 377 bar, reacts?
Fischer comb.) purity? (powder, liquid, powder)
morpholinium oleate Battelle prep. (Aldrich/ some reacts @ latm(@?)
Fischer comb.) purity? part. liquid 377-585 bar
morpholinium perfluorobutyrate Battelle prep misc. 204 bar, #
(solid, liquid, dissolution)
morpholinium perfluorooctanate Battelle prep misc. 133 bar, #
(> 80% Straight chain) (solid, liquid, dissolution)
morpholinium dodecylbenzene Battelle prep (from ~1. ~01. (to part?) 183-587 bar
sulfonate Conco AAS-98s) (waxy solid, liquid)
N-soya-N-ethyl morpholinium+ ICI (Forestall) insol. to 388 bar
CH3CH2S04- (gel-like, liquid), ##
N-cetyl-N-ethyl morpholinium+ ICI (Atlas G-263) insol. to 565 bar
CH$H~SO4- (waxy solid, viscous liquid)
 The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990 Solubility of Surfactants and Related Molecules 55

Chemical Identification Source & Trade Name Observations

(continued)

B-hvdroxyethyl benzyl “Coca” cs insol. to 377 bar

’ imidazolinium chloride (very vise. liquid, liquid)
diethyl heptadecyl imidazoline cs insol powder to 377 bar
ethyl sulfate
lauryl pyridinium chloride CS insol. to 377 bar
(powder, paste)
[NH(CH.$H2OH)# laurate- cs (purity?) sl. sol. 169-388 bar
[NH(CH~CH~OH)~l’stearate cs (purity?) part. 169-377 bar
[NH(CH$H20H)# linoleate- Henkel (Standamid SOD) sl. sol. (to part.) liquid 169-388 bar
(+6% diethanolamine)
monoisopropanolamine/lauric acid Mona (Monamid LIPA) sl. sol. to part. 169-388 bar
(+3% monoisopropanol amine) (powder, liquid)
monoisopropanolamine/alkyl Witco (Witconate P-1059) sl. sol. liquid 169-388 bar
aryl sulphonate
isopropanolamine dodecylbenzene Continental (Conco AAS sl. sol. liquid 280-388 bar
sulphonate Special 3)
[NH(CH2CH20H)# (lauryl sulfate)- Henkel (Standapol T) insol. to 388 bar, powder to gel
(-powder, paste)
N-stearoyl ethylene diamine cs sl. sol. tar 169-377 bar
formate
F(CF,CF,),CH,CH,SCH,CH,N(CH&]+ DuPont (Zonyl FSC) sl. sol. powder 388 bar
W3~41-

W
I
[R- (C-NH -CHH,CH,CH,-N-CC2H5)2]2+
I Scher (Schercoquat DAS) insol (tacky solid) to 388 bar
I: C”3

2 (CH,CH,SO,)-
where
R = dimer of oleic acid (linked at double bond)

ii i
F- (C-NCH&H,CH,y CH3
-Phenyl),12+ Scher (Schercoquat DAB) insol. (tacky solid) to 388 bar
2cr
where
R = dimer of oleic acid (linked at double bond)
1-propanaminium, 3- ( (perfluoroalkyl 3M (FC-135) insol. to 388 bar
C&a sulfonyl) amino)-N,N,N-tri- (powder, wax)
methyl, iodide

Related but Partially Unknown Materials

perfIuoroalky1 pyridinium salt Atochem (Forafac 1098) insol. powder to 388 bar, swells
trimethyl fluoroalkyl ammonium ICI (Atsurf F-21) sl. sol. (powder, paste 160 bar,
iodide powder 530 bar)

Amines (note: O-15 minutes time frame)

bis (2-ethylhexyl) amine Fluka misc. 213-278 bar
n-coca-propylenediamine cs sl. sol. 278-377 bar
(84% diamine) (vise. liquid/wax, wax), ##
n-hexadecyl morpholine Air Products (DABCO CEM) misc. 202 bar

Alkyl Phosphates
Nas (2-ethylhexyl)~(P301& cs insol. gel, 278 bar, sl. sol? 377 bar
Na5 bwW3Ot0)2 cs insol. waxy gel 278 bar
~m2~2woxmH$~2 DuPont (Zonyl FSP) part. 386 bar
wa~2w2R~xmH4,pcoXoNH4) ( waxy solid, liquid, powder)
Rf = WFzCF334
56 Consani and Smith The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990

Chemical Identification Source & Trade Name Observations

(continued)

Ethyl triphenyl phosphonium Aldrich insol powder to 585 bar

bromide
Related but Partially Unknown Materials
perfluoroalkyl phosphoric ICI (Atsurf F-12) Part? (fog) 278-388 bar
ester anionic surfactant (vise. liquid/wax, wax)

Silicon Containing Materials

polyalkyleneoxide methyl Union Carbide (L-5340) sl. sol. liquid 169-377 bar
siloxane copolymer
polyalkyleneoxide modified Union Carbide (L-77) nearly misc. liquid 278 bar
polydimethylsiloxane

(CH,),Si-0 WHd3

0 -(C,W), - B Goldschmidt (ABIL B8842) sl. sol. liquid 388 bar

same as above, different x Goldschmidt (ABIL B8843) sl. sol. liquid 169-388 bar

CH3 C’43

I I
(CH,),Si-0 Si-0 Si -0 SNCW3
I I
tCH2)3
Goldschmidt (ABIL B8873) sl. sol. liquid 278 bar
C”3
tli I
O-
f
~C,&, -(C,hP), --H

Eo 35
~0 - 65 by weight

(CH,),Si-0 WH3)3
Goldschmidt (ABIL 9801) part. liquid 384 bar

Miscellaneous Compounds, Mixtures of Compounds, or Partially Proprietary Materials

fluorinated alkyl alkoxylates > 90% 3M (FC-171) cloudy? misc. 169-377 bar
fluorinated alkyl sulfonamides < 10%
fluorinated alkyl alkoxylates > 80% 3M (FC-760) misc. 158 bar, cloudy?
fluorinated alkyl sulfonamides < 20%
C2’-‘5
I
C~.EM~~)+ISO~-N 3M (FC-10) misc. 169 bar
I
C2H40H

i
95%
‘Vi 7SOd 3M (FX-12) misc. 109 bar, (-#)
I
C2H5
The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990 Solubility of Surfactants and Related Molecules 57

Chemical Identification Source & Trade Name Observations

(continued)

aminopolyfluorosulfonate Atochem (Forafac 1159) misc. 136-160 bar

(waxy powder, liquid, dissolution)
polyfluoroalkyl betaine Atochem (Forafac 1157) sl. sol. 278-377 bar
(waxy solid, liquid)
perfluoroalkyl betaine ICI (Atsurf F-41) part? 388 bar (wax, powder)
perfluoroalkyl amphoteric ICI (Atsurf F-42) insol. tacky solid to 388 bar
non-ionic fluorosurfactant ICI (Atsurf F-3 1) sl. sol. (?) 388 bar
ethoxylated perfluoroalkyl ICI (Atsurf F-35) sl. sol. 169 bar, part. 278 to
surfactant 388 bar
n H 0

[CH,(CH,),,C-0 -CH,CH,N-C-CH,-

NCsHsl+Cl- Witco (Emcol E607L) insol. waxy powder to 388 bar

i.e., a pyridinium chloride
lauric acid monoethanolamide cs sl. sol. 169-377 bar
(chips, powder)
N-P-hydroxyethyl stearyl imidazoline cs sl. sol. solid 278-377 bar
sodium hydroxyethyl cocoamidoethyl Henkel (Velvetex GC-88) insol. waxy solid to 388 bar
carboxymethyl acetate
sodium sulfated glycerol cs insol powder to 377 bar
monolaurate
dry cleaning formulation Caled Signal (as received) sl. sol. 169 bar,
(Valcene HMC) part. 278 bar to 432 bar
fluorinated “amine oxide” Atochem (Forafac 1183) sl. sol. 169-454 bar
(waxy powder, powder)
linear alkyl-(PEO),-S04- NH4+ GAF (Alipal CD- 128) insol powder to 388 bar
polyacrylamidomethyl propane Henkel (Cosmedia Polymer insol. (brittle flakes) to 388 bar
sulphonic acid HSP-1180)

Qualitative solubilities of materials in carbon dioxide at 50 “C

Legend
Ins01 Decompression of saturated solution did not result in darkening of the carbon dioxide phase due to precipitation of
dissolved solid.
sl. sol. Decompression of saturated solution resulted in darkening of the carbon dioxide phase due to precipitation of
dissolved solid. Majority of the surfactant is still undissolved.
part. A part of the surfactant (20 to 80% by viewing) dissolved into the carbon dioxide fluid.
misc. Complete dissolution of the surfactant into the carbon dioxide fluid.
liquid Liquid definition also includes suspensions.
vise. viscous.

morphological changes are generally noted by parentheses as in:

(state at 1 atm & 25 “C, state at higher pressure & 50 “C, state at still higher pressure & 50 “C, etc.)
* indicates that this solid initially swelled upon addition of water
# indicates that this pressure was close to the minimum pressure need for total solubilization
### Coca, tallow, and soya, refer to hydrocarbon groups having carbon length distributions similar to the corresponding
acids.

When a significant amount of precursors were known to
be in the surfactant, and no effort was made to remove
them, this is noted.
Equipment and Experimental Paradigm
Solubility was determined by simple visual inspec-
tion, using a high pressure stainless steel cell equipped
with sapphire windows. The cell had a volume of 23.9
cm’, and an observation path length of approximately 7.6
cm. About 1 gm of surfactant was added to the cell and
the temperature was then raised to 50 “C. The cell was
flushed and pressurized with carbon dioxide to a particular
density (using a Varian 8500 pump) and the contents were
then thoroughly mixed using a magnetic stirrer.
Observations regarding solubility were then made, after
which additional carbon dioxide was added to allow obser-
vations regarding solubility at higher fluid densities.
Observations regarding solubility were usually made lO-
15 minutes after mixing; a slower dissolution process or a
reaction of the surfactant/carbon dioxide/residual solvent
in a longer time frame could result in different observa-
tions, However, in the cases where larger observation
times were used (>2 hr), the results were unchanged.
Because the purpose of the experimentation was to
identify a surfactant that would form a w/o microemulsion
58 Consani and Smith
in supercritical carbon dioxide, a l/16-inch stainless steel
tubing port for the addition of water was connected to the
cell also. As will be shown below, we have found that it
sometimes takes very little water (or other solvent) to
drastically alter the solubility properties of substances in
carbon dioxide. The tubing associated with this inlet port
is thus a potential source of water contamination, but the
authors believe that since this contamination was no
greater than 0.05% by volume (in the worst case), our ob-
servations on the solubilities are largely unaffected. A
greater source of contamination is believed to be residual
solvents from surfactants that were difficult to completely
dry, or from powder surfactants (used as received) that we
did not attempt to dehydrate.
RESULTS AND DISCUSSION
Our solubility results are presented in Table I. We
describe the solubility of surfactants as slightly soluble,
partially soluble, or miscible. Compounds were arbitrar-
ily fit into nine categories: acids, salts of acids (anionics),
polyoxylated materials, hydroxy compounds, quatemary
salts, amines, alkyl phosphates, silicon containing mate-
rials, and miscellaneous compounds/mixtures of com-
pounds/partially proprietary materials.
Previous work on the solubility of solids in low
pressure non-polar gases has shown that the solubility of
a substance is often proportional to the vapor pressure of
the substance. At higher gas densities, solubilities are in-
fluenced by intermolecular forces that become progres-
sively more important with increasing fluid density.
Consequently, for higher molecular weight compounds,
and for the temperature and densities discussed here, it is
reasonable to suppose that solubility increases with pres-
sure. Not all high molecular weight surfactant-like mate-
rials follow this generalization at this temperature (e.g.,
stearic acid),“J* but many appeared to and this simplified
view seems a good first approximation.
Therefore, if a substance was only partially soluble,
the formation of a “fog” upon slight decompression is
taken as evidence for some degree of solubility; this was a
helpful insight if the majority of the surfactant introduced
into the cell appeared to be undissolved. This was the ba-
sis for designating a surfactant as either slightly soluble
(sl. sol.) or insoluble (insol.). Because such observations
are qualitative, it is uncertain precisely how much mate-
rial was dissolved, though certainly the amount indicated
by a “~1. sol.” reading is well above that required for su-
percritical fluid chromatography work with standard detec-
tors (~10~~ M) and is quite likely to be observable using
infrared detection.‘>-‘*
It should also be remembered that in the case of sur-
factants designated as “~1. sol.,” and sometimes “part.
sol.,” one may not always assume that the dissolved ma-
terial was indeed the identified surfactant. Some of the
Chem Services materials were of unknown purity.
Furthermore, most of the surfactants had to be dried of
The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990
solvents, though this was done convincingly in most
cases. Beyond the question of impurities, or remaining
traces of solvent, many industrial surfactants consist of a
range of oligomers, and often contain -l-5% residual pre-
cursor. Therefore, an observed “slight solubility” could
potentially be due to a number of contributing factors.
Similarly, a substance which is reported as “nearly misci-
ble” may instead be completely miscible, for similar rea-
sons.
Additionally, one should remain mindful of the pos-
sibility of the reaction of surfactants with carbon dioxide.
Many aliphatic amines and nitrogen-containing hetero-
cyclics may react with carbon dioxide to form carba-
mates,1g2*19for example, though it must be recognized
that carbamates are not known for thermal stability.
Quatemary salts that are not (virtually) 100% thermally
stable will provide a small (equilibrium) amount of the
corresponding amine and acid. The resultant amine would
then be available for reaction with carbon dioxide solvent
to yield the (presumably thermally stable) carbamate.
Considering the acid strengths of the appropriate species
involved, as expressed by pKa’s in aqueous solution, this
is believed unlikely for most quaternary salts under the
conditions discussed here (temp = 50 ‘C, anhydrous sol-
vent, P < 600 bar).
Most of the surfactants were evaluated using carbon
dioxide at fluid densities such that the more dense solid ox
liquid surfactant remained on the cell bottom. However,
at higher pressures it was sometimes the case that the sur-
factant would float, and observations regarding the
“slight” or “partial” solubility for that particular combina-
tion of surfactant and CO2 density were estimated. A
more common situation was a solid which would simply
liquify, or display morphological indications of becoming
swollen, preclu.ding definitive statements on its “partial’
solubility. As these changes may possibly be indications
of new structures (reversed hexagonal, lamellar, etc.:
which are of scientific interest, 2o-24many of those obser
vations are reported in Table I.
Solubility of Surfactants and Related Corn,
pounds in Carbon Dioxide
As was probably to have been expected on the basi!
of prior work,‘v3 most ionic surfactants (e.g., salts 0
acids, quatemary compounds, alkyl polyphosphate salts
were found to be relatively insoluble in carbon dioxide a
50 ‘C and densities (S, -1 gm/mL. In general, solubiliza
tion of ionic solids in solvents can occur by three mecha
nisms: by solvation of ions, by ion-pair solubilization, o
by solubilization of multimers.
For ions to form in carbon dioxide fluid, the ionic
salt would have to have an exothermic interaction wit1
the solvent greater in absolute value than the energy hold
ing the ionic surfactant together. In the standard applica
tion of Hess’s law to the dissolution of inorganic solic
salts in water, we see there is a delicate balance betweei
these two large opposing forces, the result of which gen
The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990
erally governs whether an ionic salt (containing monova-
lent ions) dissolves in water.25 For carbon dioxide as a
solvent, the situation is different in that the solvation in-
teraction between carbon dioxide and ions is generally not
as strong as the solvation interaction of water and ions,*&
29 and this energy is insufficient to overcome the lattice
energy of the salt. Hence, ionic dissolution in carbon
dioxide is not favored for common ionic compounds,1,3
and most likely not favored for most ionic surfactants.
The other two processes of dissolution, ion pair sol-
ubilization and solubilization of multimers, remain, and it
seems unusual to the authors that surfactants were not
more soluble. An examination of the hydrophilic/hydro-
phobic representation of surfactants may be useful. Many
of the studied surfactants have hydrophilic moieties
(alkanes, perfluoroalkanes, etc.) which, if considered by
themselves, would be soluble in carbon dioxide at rather
easily attained densities. As for the other part of the am-
phiphile, the hydrophilic moieties were often groups such
as sulphonates, carboxylic acids, or q&ternary ammonium
cations, coupled with simple ions such as Na+, K+, Cl-,
or I-. Though the authors are not aware of thermody-
namic data for the interaction between carbon dioxide and
the appropriate ion pairs, gas phase data does exist for the
interaction of these ions with carbon dioxide.2”29
The enthalpy of interaction of these ions with carbon
dioxide is found to be approximately 50-60% of what the
interaction might be in water. While this is a significant
decrease over what is obtained using water as a solvent,
even beside the point that the solvation numbers for car-
bon dioxide may be lower and that the secondary solvation
enthalpy for,carbon dioxide will also be lower (see ref. 30
for an example of the importance of the secondary solva-
tion layer), it does not preclude the possibility for solubi-
lization by solvation of ion pairs or multimer aggregates.
Using the limited information on enthalpy and entropy
available (ref. 29), the Gibbs energy preference of an ion
for water over carbon dioxide at 50 “C and 1 atm,
[AG50”(M+‘- + H20 = M(H20)+/-) -AG50”(M”- + CO2 =
M(CO#‘-)], is NH4+ (by --8.7 kcal/mol) > Na+ (-7.7) >
K+ (-7.3) > Cl- (-6.9) > SG3- (-6.1) > NO*- (-6.0) >
Cs+ (-5.9) > I- (-5.1) > C2H5NH3+ (-4.7) > CH3NH3+ (-
4.0) > o*- (-.3).
While these are large energy differences when consid-
ering the solubility of ionic compounds in solvents, in-
creasing the pressure of carbon dioxide on a reaction that
has carbon dioxide as a reactant will make the Gibbs free
energy change more negative by amounts that will pro-
mote solvation to a limited degree. For example, assum-
ing that the equilibrium constant is approximately inde-
pendent of pressure, an increase of 500 atm causes a favor-
able Gibbs free energy change of -4.0 kcal/mol, while
1000 atm will cause a favorable change of -4.4 kcal/mol.
This suggests that, for surfactants having a reasonably
10~ lattice energy (e.g., those containing large ions, I-,
etc.), increasing the pressure of carbon dioxide could con-
Solubility of Surfactants and Related Molecules 59
ceivably result in conditions favoring solubilization by
ion pair or multimer aggregate solvation. The situation
could be even more favorable if the solvated aggregate has
hydrogen bonding or other specific bonding that was pre-
cluded for the pure surfactant in the solid phase. In the
end, however, the heats of solvation for surfactants at the
relatively modest pressures of carbon dioxide used here
were apparently insufficient to cause significant dissolu-
tion for the majority of ionic surfactants. This is evident
from the results of the “salts of acids” and “quatemary
ammonium salts” sections, which indicate that most ionic
surfactants are relatively insoluble in carbon dioxide.
Notable exceptions to the above observation of low
solubility for ionic surfactants were selected members of
the morpholine salt family, some of which displayed high
solubility in carbon dioxide (interestingly, these materials
liquified before developing significant solubility in the
carbon dioxide phase). It must be noted that the acid of
the morpholinium quaternary salt must be strong enough
to prevent significant dissociation; otherwise the destruc-
tion of the surfactant is possible, producing the conjugate
acid and morpholine carbamate (morpholine will react
rapidly with carbon dioxide, producing morpholine carba-
mate, even at 1 atrn).ls31
Observations on the solubility of morpholinium
alkanoates were complicated by the uncertain purity of the
compounds. The solid morpholinium myristate, when
prepared in ether or in pentane, gave a persistent acid band
absorption in the infrared spectrum of the powder, indicat-
ing that the precipitation yielded either a mixture of salt
and excess acid, or a “mixed salt.” The nature of the salt
was not determined, but the general problem has been no-
ticed previously,32 and chloroform was suggested as a sol-
vent that would produce a quaternary salt with only car-
boxylate absorptions; we tend to agree, but the salt was
so soluble in chloroform that isolation was difficult, and
time did not permit further work. The morpholinium
myristate prepared in ether or pentane was never com-
pletely solubilized in carbon dioxide; a very fine powder
always remained. Perhaps slight amounts of water impu-
rity caused metathesis and subsequent precipitation of a
small amount of bicarbonate (see “Additional
Complications” section), or the morpholine myristate
equilibrium slowly provided enough morpholine .to make
a visible amount of carbamate. Morpholine carbamate it-
self was found to be essentially insoluble up to 574 bar.
The liquid morpholinium oleate was made by direct
combination of morpholine and oleic acid and was not fur-
ther purified. It also showed a tendency. to form a small
amount of white powder (which became dispersed in the
liquid morpholinium oleate) when exposed to carbon diox-
ide. This powder was, again, probably morpholine car-
bamate, possibly made by excess morpholine or the par-
tial decomposition of the morpholinium oleate to give
morpholine.
60 Consani and Smith
In light of these difficulties, a stronger chemical
acid/morpholine base pair was sought to obtain a more
easily purified compound, and to avoid any possibility of
reactions of the surfactant and the continuous phase. The
perfluorinated alkanoic acids are much stronger acids than
the alkanoic acids, and their morpholinium salts were
consequently much easier to isolate and purify (with chlo-
roform as a solvent). Preliminary infrared studies of mor-
pholinium perfluorooctanate dissolved in carbon dioxide
(35 to 50 “C, up to 448 bar) have demonstrated no in situ
carbamate formation.
The solubility of these compounds is not solely due
to the cation, as a morpholinium sulphonate and two
morpholinium sulfates were found to be relatively insolu-
ble. Additionally, morpholinium chloride was insoluble
to 576 bar, while morpholium iodide was slightly soluble
between 169 and 576 bar. These results are consistent
with the apparent higher lattice energies of sulfonates and
sulfates (see comments on solubility parameters below)
and the expected decrease in lattice energy upon going
from a chloride to an iodide.25
Compounds one might think of having some
prospects of being molecularly solubilized in carbon diox-
ide (e.g., cobalt stearate, lead stearate, nickel oleate), or
solubilized as intermolecularly bonded multimers (e.g.,
aluminum palmitate),23-24 were found to be insoluble or
only slightly soluble.
Extensive reports in the literature on “pre-micellar”
carboxylate/acid aggregates20*21~23~24~33-38 prompted exper-
imentation with such mixtures. A “pre-micellar aggre-
gate” is defined as a collection of molecules, generally in
the range of three to ten, associated in solution. Only a
few systems have been investigated with any thorough-
ness, but the aggregate is generally composed of surfac-
tant molecules (alkali carboxylates, amines, etc.) some-
times linked by water and/or alcohol. They form stable
solubilized species, and are subsumed (along with “true”
micellar solutions) in an area of the phase diagram repre-
senting visually clear, apparently homogeneous solutions.
Boundaries in the triangular phase diagram between the
micellar and pre-micellar areas for a carboxylate/acid sys-
tem have actually been reported.39 The nature of pre-mi-
cellar aggregation and its relation to the “true”micellar
phase is receiving greater attention with more sophisti-
cated techniques,38*4W3 but is not yet well studied.
The addition of stearic acid to lithium stearate (2:l)
and to cobalt stearate (1: 1) did not appear to greatly in-
crease the solubility of the salt; there was significant
swelling of the solid phase(s?) when the water addition
was small, followed by some shrinking of the solid phase
upon further addition of water. It should be noted, how-
ever, that stearic acid itself is only “~1. sol.” in this pres-
sure range, beginning at -142 bar and extending to 585
bar (see also refs. 11,12). As well, we note that even
10% stearic acid does not increase solubilization of copper
stearate with cetane as a solvent,44 so the case of stearate
The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990
is probably peculiar, most likely due to the length of the
linear alkyl chain and the subsequent stability of the crys
talline salt. Binary mixtures of other acids and salts be.
haved similarly; lithium myristate(0.3)/myristic acid(0.7)
sodium decanoate(0.3)/decanoic acid(0.7), and nicke
oleate(0.3)/oleic acid(0.7) mixtures did not greatly increase
the solubility of the salts in carbon dioxide (though the
lithium system partially swelled with pressure, and witt
initial water addition). A 1:2 mixture of lithium perfluo.
rooctanate and peffluorooctanic acid (both > 80% straigh
chain) appeared to form long fine crystals in carbon diox,
ide, which may be the mono acid/salt compound.35
Two mixtures of ordinary hydrocarbon salts and fluo
rinated acids were tried. The presence of the fluorinatec
acid was expected to increase the solubility of the salt (i
should be noted these mixtures may be complicated b!
metathesis, and are presumably mixtures of perfluorinatec
acid, hydrocarbon acid and their salts, weighted in favor o
the perfluoro salt). A lithium stearate(0.3)/perfluro
(>80% n-)octanoic acid(0.7) mixture did not seem tc
greatly increase the solubility of the salt. A nicke
oleate(O.3)/perfluoro-(>80% n-)octanoic acid(0.7) mixture
however, was solubilized by at least 218 bar. The exten
of possible oxidation of the iron cell wall to give the fer
rous salt and nickel metal (if any) was not investigated.
The formation of carboxylic acid dimers in carbon
dioxide fluid has been suggested by workers involved ii
SFC chromatography” and in extraction processing typl
work,46 and of course self association of acids is a we1
known phenomenon in other solvents,47 so our finding
on the solubility of long chain alkanoic acids are not sur
prising and are included for comparison purposes onl:
(indeed many reports exist on the quantitative solubilit:
of acids I 11I *,45,4*>.
The comparative insolubility of n-lauryl sarcosin
indicates, apparently, that this solid remains zwitterioni
in carbon dioxide, and either the low dielectric of carbo
dioxide (1.3 to 1.5) or appropriate molecular forces wil
not support significant solubilization of the compoun
(even as multimers). These results are consistent.wit
earlier observations in supercritical fluid chromatogr;
phy‘t‘+%50 and extraction studies4 that indicated that lowe
molecular weight amino acids are usually not very solubl
in carbon dioxide at lower pressures, and that derivatizr
tion to obtain less polar compounds (more amenable t
solubilization in carbon dioxide) is needed before a signij
icant solubility in carbon dioxide is achieved.51
Apparently sulfonic acids have less intermoleculr
hydrogen bonding abilities in supercritical carbon dioxid
than the alkanoic acids, judging from the relatively lo!
solubility of dodecylbenzene sulfonic acid in carbon dior
ide (the corresponding “dodecyl” benzene precursor, Ci&:
2 85%, Conoco Nalkylene 500, can be completely sol1
bilized in carbon dioxide at 126 bar). We also note th;
methane sulfonic acid is only slightly soluble between 8
to 519 bar, with the solubility increasing as pressure ir
The Journal of Supercritical Fluids, Vol. 3, No, 2, 1990
creases. This apparent inability of sulfonic acids to hy-
drogen bond in carbon dioxide is in contrast with benzen-
sulfonic acid’s reasonably significant solubility in ben-
zene, where the formation of multimer aggregates was
proposed, 52 and with dinonylnaphthalene sulfonic acid
which has also been reported to form dimers, using hen-
zene or siloxane dimer as solvent.53
In spite of the evidence that moderate solubility oc-
curs in other solvents (as a result of aggregate formation),
this is not observed for carbon dioxide, and the sulfonic
acid group may be added to the list of groups having a
moderately detrimetal influence on the solubility of the
compound in carbon dioxide. As the two sulfonic acids
examined above are liquids, with no lattice energy to
overcome during dissolution, the insolubility may arise
from a positive enthalpy of interaction. As with other
compounds, however, partial fluorination of the alkyl
group of a sulfonic acid appeared to enhance solubility, as
C6Fr3C2H4S03H (Forafac 1033) was quite soluble (we at-
tempted to make a fully fluorinated Cs sulfonic acid from
FC-95, but the purity of the relatively insoluble product
was not convincing). Sulfonate esters of sulfonic acids
would presumably be more soluble than the acids, based
upon the corresponding situation with alkanoic acids.2
The phosphate acids appeared to have a reasonable
amount of solubility, consistent with previous work on
phosphate acids in aprotic solvents showing formation of
multimers.47
The only general information that can be gleaned
from the polyoxylated materials and limited glycols data
is that carbon dioxide will only entertain a small number
of polyoxyethylene, polyoxypropylene, or glycol units,
and extending the alkyl chain to increase the solubility of
such molecules has a limit that is quickly reached.
Though the solubility parameter model is not univer-
sally accepted for predicting and understanding solubility
phenomena in fluids, in the absence of any relevant ther-
modynamic data for surfactants, or of any other simple
practical model, some comments are in order. According
to this model the dissolution of materials is most proba-
ble when the (carbon dioxide) solvent solubility parameter
matches that of the (surfactant) solute solubility parame-
ter, though increasing the temperature to the critical solu-
tion temperature would cause dissolution in any event
(refs. 54, 55, and references cited therein). Discussing the
solubility results in the context of the solubility parame-
ter theory proves difficult, however, due to the lack of
solubility parameters for most of the surfactants shown in
Table I, but some general comments may be made.54
The alkanoate salts were mostly insoluble in carbon
dioxide, particularly those with shorter chain hydrocar-
bons, as would be expected from the high solubility pa-
rameters (19 to 21 MPa1j2) of such salts.s4,56 It is inter-
esting to note that some systems among the carboxylates,
and mixtures of carboxylates, appeared to swell with in-
creasing carbon dioxide pressure, lithium stearate for ex-
Solubility of Surfactants and Related Molecules 61
ample. Like polymer/solvent systems, it is generally ac-
cepted that dissolution of surfactants in low polarity sol-
vents may be preceded by their swelling,23,24 and this has
been proposed for lithium stearate in particular.56,23.24
Lithium stearate has a solubility parameter54,56 of -18 to
19 MPa1/2, however, and for carbon dioxide to match this
parameter would require much higher pressure (and one
may well have to raise the temperature to a critical solu-
tion temperature to achieve solubilization in any event).
The solubility of such salts is increased by using
branched or mixed alkyl chain compounds. Such materi-
als have increased molecular or pre-micellar solubility by
virtue of a lower lattice energy (i.e., a lower solubility pa-
rameter more similar to that of carbon dioxide) , or in-
crease micellar solubility by virtue of their molecular
shape (which may generally be more conducive to micelle
formation under more circumstances than straight chain
hydrocarbons).21,57T58The use of a fluorinated alkyl group
also appears to increase the solubility of salts. It may
possibly be useful to note a generalization25 from the case
of salt solubility in water; possibly if the size of the ca-
tion and anion could be made more disparate (e.g.,
R,N+F-, RNHs+I-, etc.), greater solubility could be
achieved, as this would lower the lattice energy of the salt
by the virtue of the large ion while increasing solvation
interaction by virtue of the small ion. At the present
state of understanding of the thermodynamics of dissolu-
tion in carbon dioxide, it is unclear whether this general-
ization would be of use, however.
Previously reported values54 for didodecyldimethyl
ammonium chloride (20 MPa1j2), bromide (18 MPa1/2),
and iodide (16 MPaln) indicate that iodide surfactants can
approach solubility parameter values achievable with the
lower pressures of carbon dioxide used here. We tried
none of the above compounds, but of the two quaternary
iodide surfactants reported here, dodecyltrimethyl ammo-
nium iodide and ICI Atsurf F-21, only the fluorinated
compound F-21 seemed to have any degree of solubility,
and that was only slightly soluble. This very slight dif-
ference in solubility of dodecyltrimethylammonium iodide
and ICI F-21 could also be partially attributed to the fact
that F-21 is fluorinated.
As the molecular radii of the singly charged
sulphonate and sulfates is probably at least that for I-, the
organic sulfonates and sulfates might be expected to have
low lattice energies, and thus show some degree of solu-
bility. However, an inspection of the high solubility pa-
rameters of alkane sulfates and sulfosuccinates (25-32
MPar”, ref. 54) indicate they have very high vaporization
energies, and are therefore expected to be quite insoluble
in carbon dioxide. This is the case with all the present
alkane sulfate and sulfosuccinate surfactants, and with
other similar surfactants not reported here. Even in the
relatively soluble morpholine salt family, the presence of
the sulfonate and sulfate groups inhibited dissolution.
62 Consani and Smith
Comments Regarding the Formation of w/o
Microemulsions
Though the primary emphasis of this paper is on the
qualitative solubility characteristics of amphiphiles in
carbon dioxide, the stated motivation obligates the authors
to discuss briefly the possibility of microemulsion forma-
tion in carbon dioxide. Of all the surfactants investigated,
only five were found to have unusual behavior when
mixed with water. These were FC-128, F-21, FSP, the
carboxylate mixtures and, possibly, the morpholine salt
family. In general, the first four compounds were not
especially soluble in carbon dioxide until water was added.
Upon addition of water, the solid dissolved and clear ho-
mogeneous solutions resulted. Preliminary data regarding
these solutions has been obtained, though much more
work is necessary before events can be fully understood.
Because of the importance of this subject to industry,
however, the authors will discuss some of the preliminary
details. Note that the methods employed in the majority
of this preliminary screening work did not allow us to dis-
tinguish between water dissolved in carbon dioxide and
water associated with surfactant species dissolved in car-
bon dioxide. Thus, the following water-to-surfactant
(w/s) ratios reflect those for -1 gram of surfactant in the
entire cell volume (23.9 mL) and are uncorrected for water
that may be solubilized in carbon dioxide independent of
the surfactant.
The light-tan FC-128 powder dissolved very slowly
upon addition of water to FC-128 in carbon dioxide.
Rapid addition of water resulted in the production of a
slow dissolving jelly-like mass of water and surfactant.
With time, this would dissolve and successive additions of
water would eventually dissolve the remaining powder.
With an apparent w/s -7, a laser scattering characteristic
length of between 11.2 nm (280 bar) and 8.5 nm (397
bar) was found, implying the existence of micelles or pre-
micellar aggregates. Preliminary near-IR studies on water
absorptions were inconclusive but not supportive of the
existence of a reverse micelle containing a water core.
The general insolubility of water soluble proteins and
dyes at higher pressures and at much higher apparent w/s
ratios indicated no solubilizing power associated with mi-
cellar aggregates, however.
Similar to FC-128, DuPont FSP gave a slow dis-
solving jelly-like mass upon quick addition of water to
the carbon dioxide solution. A homogeneous.phase ex-
isted between an apparent w/s -5.9 and -8.3 at P-487 bar.
Methyl red dye was soluble at an apparent w/s -8.27 at
450 bar pressure.
As with the previous two compounds, ICI F-21
product formed a slow dissolving jelly-like mass upon ad-
dition of water between 450 to 500 bar, with the clearest
solutions between 540-582 bar. Myoglobin and pepsin
were insoluble at w/s -12 up to 596 bar and 559 bar, re-
spectively. Methyl red and thymol blue were soluble
with an apparent w/s -11, near 582 bar. Preliminary mid-
The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990
and near-IR work was also inconclusive for water con
formation, at an apparent w/s -11 at 538 bar.
Addition of water to a 2:l mixture of perfluorinatec
octanoic acid/lithium perfluorooctanate caused significan
dissolution of the solid at -388 bar, with maximum
w/Li+ ratio near 6 to 7. A lithium stearate(0.3)/perfluo.
rooctanic acid(0.7) mixture resulted in a maximum w/s ra.
tio of near 8 to 9 at -502 bar. The order of magnitude o
these semiquantitative values indicates pre-micellar aggre.
gation. The other binary mixtures mentioned in the solu
bility section of this paper did not appear to significantl]
dissolve upon addition of water, although some small dis
solution may not be excluded on the basis of the presen
observations.
Increasing amounts of water could be dissolved in the
homogeneous morpholine perfluorooctanate solution a:
the pressure rose up to a maximum of 270 bar; beyonc
that, increasing pressure caused increasing phase separa
tion. A homogeneous solution resulted when water wa!
added, from an apparent w/s maximum of -1.3 (at P q
176 bar) to an apparent w/s maximum of -5.8 (at P = 27:
bar). Pressure higher than this caused phase separation
A homogeneous solution of 1 c w/s < 6 failed to solubi
lize myoglobin, suggesting the absence of an inverse mi
croemulsion. Using a morpholinium perfluorobutyrate
which has a shorter fluoroalkyl group, resulted in mucl
smaller amounts of water being solubilized. The maxi
mum of the w/s ratio vs pressure curve occurred roughl!
at an apparent w/s = 0.7 and 327 bar. Pressures highe
than this caused phase separation.
At present, we believe we have tentative evidence fo
solutions of pre-micellar aggregates or partially hydrates
ion pairs. The latter possibility may arise as a result o
the higher pressure of carbon dioxide used; the energy o
interaction of carbon dioxide with, for example
Na+(H*O),, is small compared with the interaction o
HZ0 with Na+(H20)n,38 but the interaction difference getl
smaller as the first coordination sphere fills with water
and the former equilibrium is forced with greater carbon
dioxide pressure. The slight possibility of unstable dis
persions also remains 59 but seems unlikely under the pre
sent circumstances. The implication of our result
(indicating small molecular aggregates) is also consisten
with general observations that reverse micelles in non
aqueous solvents, especially those made by quatemary SUI
factants, are usually somewhat smaller than “normal” mi
celles, both with and without water.58,60
Except for those surfactants listed above, a genera
observation would be that adding water to solutions o
surfactants in carbon dioxide generally resulted in phas
separation as evidenced by the formation of fog in the so
lution, while adding water to (an insoluble) surfac
tam/carbon dioxide mixture merely resulted in an insoln
ble wet surfactant in carbon dioxide. It should be recog
nized that our generally negative results for most surfac
tams do not preclude the formation of micelles for thos
The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990
surfactants under conditions different from our experimen-
tal paradigm. For example, in the case of some soluble
surfactants, if formation of a fog upon addition of 0.05 to
0.1 rnL of water occurred, no further water was added; thus
if higher w/s ratios were necessary for complete solubi-
lization of the solid/liquid at that pressure, a not unknown
situation, potentially useful surfactants escaped detection.
Similarly, if higher concentrations of surfactants (than
used here) were necessary for complete solubilization of
the solid/liquid, also not an unknown situation, this also
escaped notice. We did not attempt to vary other condi-
tions such as temperature or pH, or to introduce structure
making or breaking ions in the added water, etc.
Comments on Enhancement of Reverse Micelle
Formation
The question arises, how may one enhance the possi-
bility of reverse micelle formation in carbon dioxide?
Though the authors do not object to science by serendip-
ity, or taxonomy, it seems that more work on the ther-
modynamics of reverse micelles would have been greatly
helpful in guiding the way. A reverse micelle is, thermo-
dynamically, a very fragile construct.20~22~58,6It owes its
existence to a rather large variety of thermodynamic
terms, of which only a few are known. Of the studies
that have been published, it seems to be a consensus that
the formation of reverse micelles in non-polar solvents is
an enthalpically driven process.41Jja
Accordingly, to achieve micellization, any conceiv-
able change that would make more negative the overall
enthalpy change for micellization could be investigated.
An important consideration in the formation of micelles
for ionic surfactants is the ion charge-water dipole interac-
tion, as was discussed previously. Another important
unifying force in micelle stabilization is the alkyl chain
Van der Waals interactions. For the present (mostly fluo-
rinated) surfactants, we note that such micelle promoting
forces are lower for fluoroalkyl/fluoroalkyl interactions
than alkyl/alkyl interactions,61-65 and the solubility of
fluorocarbon surfactants for carbon dioxide may indicate
there is a competing interaction between carbon dioxide
and the fluorocarbon chains. Increasing the possibility of
micelle formation for these surfactants could be as simple
as increasing the fluorocarbon chain length, or branching
the chain. More significant changes to increase the chain
interaction energy may be necessary, however. Such
changes include introducing some alkyl groups (e.g., hy-
drophilic end-(CH2),,-(branched-CF2)m-CF3, where n, m
< 8), or introducing groups onto the alkyl chain that have
specific bonding to groups on adjacent chains, etc.
The magnitude of the entropy of micellization is gen-
erally considered to be a minor factor in the formation of
reverse micelles in non-aqueous systems, and generally
believed to be positive in sign, though some negative
ASS have been reported. 6o Increasing the temperature
would presumably help micelle formation, then, though
to a rather small degree. Anything that increases the in-
Solubility of Surfactants and Related Molecules 63
teraction between carbon dioxide and the hydrophobe
chain, without getting large enough to inhibit hy-
drophobe/hydrophobe interactions in the micelle, would
tend to create a more positive enthalpy of micellization
(c.f. wateP); this may be relevant in the case of the fluo-
rocarbon surfactants, judging from the unusually large
solubility that fluorocarbon surfactants have in carbon
dioxide. Generally both anhydrous surfactants and hy-
drated surfactants have a large variety of thermotropic
phases, and increasing solution temperature could have a
favorable impact on the enthalpic stability of micellar so-
lutions relative to the solid phase as we11.22
Though we have not attempted to do so, calculations
of packing parameters or R values,21J8 or other thermo-
dynamic models,22 might prove helpful in selecting sur-
factants or in designing variations of those surfactants that
appear to be promising.
Additional Complications
An interesting peculiarity of carbon dioxide as a fluid,
as opposed to hydrocarbons or inert gases, is the relatively
strong interaction between carbon dioxide and water. The
vast majority of water dissolved in carbon dioxide should
presumably be present as a loosely hydrated molecule,
provided the water is not preferentially solvating a surfac-
tant or participating in the core of a micelle. Since no in-
teraction of water and carbon dioxide (at 50 “C) known to
the authors could rival the interaction of water with water
(witness the fact carbon dioxide and water are not misci-
ble), the water/carbon dioxide complex or solvate should
not prevent bulk water core formation in a micelle. If the
temperature were low enough, of course, solvates of
H9203 and polyethers surfactants67~68and/or clathrates of
water and carbon dioxide could form,69 but this should be
of little concern at 50 “C.
With the addition of water to the surfactant/carbon
dioxide mixture, additional complications for some surfac-
tants occur as a result of carbonic acid production.
Because of the weak acidity of carbonic acid, metathesis of
the surfactant counter ion (HCOs- for X-) is unlikely in
most cases. One exception would be for the alkyl car-
boxylate ion, where an inspection of pKa’s for H2C03 and
RCOOH for aqueous solution implies that the formation
of RCOOH and MHCOs in wet carbon dioxide is possi-
ble. If this occurs, it may be one reason why these pre-
liminary experiments show pre-micellar aggregates are
more readily formed with fluorinated acids than with ordi-
nar.y hydrocarbon acids, as the fluorinated acids are
stronger (as well as more soluble).
Other chemical reactions may occur in the case of
amines. For those amines stable enough not to form car-
bamates, quaternary salt formation becomes possible. For
example, n-hexadecyl morpholine may react with water
and carbon dioxide to yield the quatemary bicarbonate salt.
The categories under which we list surfactants that have
amine groups are therefore not necessarily indicative of
the final material tested for w/o microemulsion formation
64 Consani and Smith The Journal of Supercritical Fluids, Vol. 3, No. 2, 1990

under high carbon dioxide pressure. It may be possible to
take advantage of this reaction by initially quaternizing
the nitrogens of multifunctional materials (Deriphat’s,
Hamposyl’s, etc.) with acids that might help increase the
possibility of solubilization in carbon dioxide
(perfluorooctanoic acid, for example). Finally, the hy-
drolysis of some surfactants is known to occur under
warm acidic conditions: the alkane sulfates are a very well
known example. We assumed the extent of hydrolysis
was small as quick observation times and moderate tem-
peratures were used, so our observations on the absence of
useful microemulsions for such compounds are probably
unaffected.
CONCLUSIONS
Observations on the solubility of over 130 surfac-
tants in carbon dioxide at 50 “C and over the pressure
range of 100-500 bar have been presented. In general, the
solubility of high molecular weight surfactants is consis-
tent with previous generalizations concerning functional
groups on shorter chain molecules.2 Adding to those gen-
eralizations, we have found that the sulfonic acid group
has a detrimental influence on the solubility of a com-
pound in carbon dioxide. In addition, the authors note the
apparent compatibility between fluorinated hydrocarbons
and carbon dioxide. Surfactants containing fluorine-car-
bon bonds invariably tended to dissolve at lower pressures
than the corresponding hydrogenated substances.
More interesting was the discovery of a cation
(morpholinium) and several anions (carboxylates) that can
form ionic compounds of significant solubility in dry car-
bon dioxide. It is difficult to believe that a large number
of compounds of a derivative nature would not also have
significant solubility in carbon dioxide. This is of partic-
ular note, as carbon dioxide has a distinct proclivity
against the dissolution of ionic compounds.
In preparing this paper the authors regrettably note
the lack of thermodynamic data on the interaction of com-
pounds with carbon dioxide (except for hydrocarbon indus-
try related materials) when compared with the state of
knowledge for water, a near-cost competitive rival solvent
(excluding capital costs for high pressure equipment).
Though predictive models of solubility are instructive and
quite useful for the majority of compounds,7T8,70 more
work on the thermodynamics of solution species and gas
phase thermodynamic values for ion/carbon dioxide inter-
actions2”30 is now necessary for a better understanding of
the present results.
Regarding. the possible formation of w/o microemul-
sions in carbon dioxide, this work reinforces the unstated
notion that microemulsions using commercial surfactants
are much more readily formed in other low polarity fluids
(alkanes, xenon, etc.), than in carbon dioxide. We believe
that the reasons for this extend beyond the role of CO2 di-
electric constant, which is clearly a major factor for super-
critical alkanes.” Still, four surfactants were discovered
that have unusual solubility properties in carbon dioxide;
they are soluble only when water is present. One other
surfactant family that is soluble in carbon dioxide, the
morpholinium perfluoroalkanoate series, is able to absorb
water to a small degree. With the discovery of ionic
compounds that are soluble in pure and water saturated
carbon dioxide, a wide variety of physical and analytical
techniques and processes may become possible or have
wider utility; for example, ion exchange,72 or electro-
chemical processes utilizing Nafion (DuPont), or PFSI
(Dow) type ionomers (e.g., batteries, electrolysis cells,
etc.).73-74 The exciting properties of reverse micelles and
microemulsions in supercritical alkanes and rare gases
would be of greatly enhanced practical value if comparable
systems could be created in carbon dioxide.75-79
Under the present conditions of temperature and con-
centrations we assume these compounds exist as pre-mi-
cellar aggregates, though the existence of hydrated
monomers cannot be excluded. The extent of nucleation
of such aggregates to form reverse micelles with a use-
fully large water core (under the present conditions) ap-
pears to be small. Since many modifications can be con-
ceived that would likely help produce such a situation, the
authors feel relatively optimistic that eventually such sur-
factants will be identified.
ACKNOWLEDGMENTS
We wish to thank the U.S. Army Office for their
support of this work through Contract No. DAAL033-
87-K-0137. K.C. held a NORCUS (Northwest College
and University Association for Science) appointment dur-
ing the duration of this work.
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