Ind. Eng. C h e n . Res.

1992,31, 2413-2418 2413

KINETICS AND CATALYSIS

~~ ~ ~~ ~~~

Kinetics and Mechanisms of Fatty Alcohol Polyethoxylation. 1. The

Reaction Catalyzed by Potassium Hydroxide
E. Santacesaria,* M. Di Serio, R. Garaffa, and G. Addino
Cattedra di Chimica Zndustriale, Dipartimento di Chimica dell'llniversitd, Via Mezzocannone, 4,
80134 Napoli, Italy

The kinetics of fatty alcohol ethoxylation has been studied by performing kinetic runs in two types
of reactors characterized by different dispersed phases. In one case gaseous ethylene oxide was
dispersed in the liquid alcohol reagent; in the other case, alcohol was sprayed into the ethylene oxide
gaseous mixture. In both cases chemical reaction rates were not affected by diffusion, in the adopted
experimental conditions. The reaction occurs through an SN2 mechanism. A kinetic model of general
utility for interpreting ethoxylation behavior has been developed. The model describes the ethylene
oxide consumption, the alcohol conversion, the molecular weight distribution, and the change with
time of the reaction mixture volume and of the ethylene oxide solubility.

Introduction pretation of kinetic runs of 1-dodecanolpolyethoxylation

Nonionic surfactants are industrially produced by
base-catalyzed reactions of hydrophobic compounds con-
taining active hydrogen, such as alkylphenols, fatty alco-
hols, fatty acids, mercaptans, and alkylamines, with
ethylene and/or propylene oxide (Schick, 1967,1987). In
spite of the importance of these products, few papers have
been published on the kinetics of polyethoxylation. In
particular for fatty alcohols, Gee et al. (1959) have found
a firsborder dependence of reaction rates on both ethylene
oxide and catalyst concentration. However, Satkowski and
Hsu (1957) observed an order of less than 1by using KOH
as catalyst at 135-140 "C. Ischii and Ozaki (1960) sug-
gested that below 130 O C , in the absence of solvents, the
reaction occurs with a mechanism involving the ionic
couple while at higher temperatures the anionic mecha-
nism predominates. Ethoxylation rates may depend also
on the fatty alcohol chain length as suggested by Satkowski
and Hsu (1957).
As can be seen, many conclusions reported in the lit-
erature are controversial. In particular, kinetic results may
be unreliable because they have normally been obtained
by interpreting curve8 of ethylene oxide added during time,
without considering diffusion limitation, the change of the
reaction mixture density, the change of ethylene oxide
solubility, the change of catalyst concentration, and, above
all, the change in the oligomer distribution. In fact, it is
interesting to observe that the use of CsOH as catalyst,
instead of NaOH, gives rise to a narrow range oligomer
distribution, as observed by Matheson et al. (1986). This
behavior is strongly enhanced in the presence of alkaline
earth metal catalyts such as barium, calcium, or strontium
compounds, as reported in many patents and papers re-
cently published (Yang et al., 1980a,b; Yang, 1980; Brace
et al., 1988, 1989).
In the present paper, a kinetic model of general validity
and able to reproduce results commonly obtained will be
described. This model will be applied here to the inter-
* To whom correspondence should be addressed.
0888-5885192/263I-2413$Q3.O010 0 1992 American Chemical Society
catalyzed by KOH. In a succeeding paper, the same model
will be applied successfully to the narrow-range eth-
oxylation obtained in the presence of a barium catalyst.
The previously mentioned kinetic model is an extension
of a model already published by Santacesaria et al. (1990)
and applied to nonylphenol polyethoxylation in the
presence of KOH.
In all cases, polyethoxylation was performed in a well-
stirred isothermal semibatch reactor. The mathematical
model developed is able to reproduce the evolution with
time of the ethylene oxide consumption and the molecular
weight distribution for different temperatures, ethylene
oxide pressures, and catalyst concentrations, by taking into
account also the change with time of the volume of the
reaction mixture and of the ethylene oxide solubility. For
this purpose, solubility and density parameters have been
determined by independent experiments.
Experimental Section
Apparatus, Techniques, and Reagents. Kinetic runs
were performed in a jacketed, 1.5L stainless steel reactor,
equipped with a magnetically driven stirrer, consisting of
a turbine connected as in Figure 1, to a holed rod, able to
develop a great interfacial area. The control of pressure,
temperature, and ethylene oxide feeding the reactor was
fully automated by a computer. The ethylene oxide con-
sumption was directly measured and recorded at each
instant with a weight balance connected to the computer,
measuring the loss of weight of the ethylene oxide bottle.
The ethylene oxide in the bottle was pressurized with
nitrogen at about 10 atm.
Also temperature and pressure were controlled and re-
corded at each instant. Temperature was kept constant
through two thermostated fluids, one for heating and the
other for cooling the reaction mixture. The heating fluid
always circulated in the reactor jacket, while the freezing
one was automatically fed, when necessary, to a coil inside
the reactor.
Ethylene oxide was automatically fed to the reactor to
keep a preset value of the pressure constant.
2414 Ind. Eng. Chem. Res,, Vol. 31, No. 11, 1992
I I A€
Figure 1. Scheme of the automized plant employed in the eth-
oxylation. A = computer; B = computer interface; C = on-off valve
for feeding ethylene oxide; D = ethylene oxide bottle; E = pressure
transducer; F = manometer; G = exit for withdrawing; H = jacketed
reactor; I = freezing coil; L = holed stirred; M = Magnedrive stirrer;
N = thermocouple. Details of the stirrer, L, are shown.
Time
Figure 2. Example of chromatogram obtained by HPLC. Numbers
are related to the EO adducts in the molecule. The f i t peak is the
excess of derivatizing agent.
Kinetic runs were made using 1-dodecanolas fatty al-
cohol and KOH as catalyst, by changing the ethylene oxide
preeaure, the temperature, and the catalyst concentration.
Samples of the reaction mixtures were taken at different
times, derivatized with 3,6-dinitrobenzoyl chloride as
suggested by Desbene et al. (19871, and analyzed by the
HPLC technique. The elution gradient technique was used
with solvent A (99/1 (v/v) = n-heptane/CHzC12-2-
propanol (95/6)) and solvent B (60/50 (v/v) = n-hep-
tane/CH2C12-2-propanol (95/5)). The sample was injected
on a 26- X 0.4-cm column of Lichrospher 100 Diol fur-
nished by the Merck Co. The solvent feed rate was l
cm3/minand the sample was eluted with a gradient of the
following type: B was increased from 0 to 100% during
the fmt 60 min, then only B was fed for 15 min, and from
65 to 80 min B was decreased from 100 to 0%. The UV
detector was kept at 254 nm.
The different oligomers were recognized by injecting
standard monodispersed samples furnished from the
Nikkol Chem. Co. and by observing a proportionality be-
tween retention times and number of ethylene oxide ad-
ducts. Figure 2 shows an example of the chromatograms
obtained.
Some kinetic runs,performed in a completely different
reactor, a ’Pressindustria type”reactor, 10-L volume, have
also been interpreted. In this case the liquid was sprayed
into the ethylene oxide atmosphere as shown in Figure 3.
Finally, also kinetic runs performed by Satkowski and Hsu
(1957) were interpreted for comparison with the kinetic
model we suggest.
As mentioned, for accurate kinetic evaluation it is im-
portant to know how the density of the reaction mixture
I 1
Figure 3. Scheme of the Pressindustria type reactor.
0 240 480
Time (minutes)
Figure 4. Kinetic behavior of nonylphenol in the ethoxylation
performed at different temperatures. The plot is related to runs
performed at 3 atm of EO by using 0.785 mol of nonylphenol and
about 0.0146 mol of KOH.
and the ethylene oxide solubility change with the extent
of reaction. For this purpose, the density of 1-dodecanol
polyethoxylate was measured with a pycnometer at dif-
ferent mean molecular weights and temperatures.
Solubility runs have been performed in the same reactor
of Figure 1using, respectively, pure dodecanol and poly-
ethoxylated mixtures treated several times with ion-ex-
change resins of the Amberlite IRC 76 type,i.e., resins with
moderate acidity, to eliminate any trace of the potassium
catalyst. Runs have been performed as already described
by Santacesaria et al. (1990).
Reagents used were of the maximum purity commer-
cially available: 1-dodecanol was furnished by Aldrich Co.,
ethylene oxide by the SIAD Co., potassium hydroxide by
the Prolabo Co., and Amberlite resins by the Rohm and
Haaa Co. The jacketed reactor was built by INOX-Im-
pianti Co.
Reaction Pattern and Kinetic Model. Santacesaria
et al. (1990) showed that, in the ethoxylation of nonyl-
phenol, the acidity of nonylphenol has a strong influence
on both the rate of the initiation step and the equilibrium
of proton transfer. As a consequence thereof, reaction ratea
are initially slow, until all the nonylphenol has reacted, and
then reaction rates increase as shown in Figure 4. In the
case of 1-dodecanol, these effects are absent; therefore, it
is reasonable to assume the same reaction constant for both
the initiation and propagation step. Then, considering the
same acidity for 1-dodecanol and the ethoxylatad oligom-
ers, as suggested by Nagase and Sakaguchi, (1961),
Stockburger and Brandner, (1963), and Lowe and Weibull,
(19541, the proton-transfer equilibrium
RO- + RO(E0)iH ROH + RO(EO)[ (1)
should have a constant equal to about 1.
With this last assumption it is impossible to describe
correctly the oligomer distribution. In particular, it is
impossible to extend the model to the description of the
 Ind. Eng. Chem. Res., Vol. 31, No. 11,1992 2415
oligomers with the substrate, other equilibria being a linear
combination of these, we have
[ROH][RO(EO);M+]
(11)
Keoi= [RO(EO)jH][RO-M+]
we can write
Keoi(mi/mo)[RO-M+]= [RO(EO);M+] (12)
It is also possible to write
071 t I [RO-M+] n
20 60 100 140 180 CKeoimj= Bo - [RO-M+]
Temperature ? C )
(13)
mo 1=1
Figure S. Density aa a function of temperature for different average
number of EO adducts. Number of adducts: (0) 0, ( 0 )2.13, (A) and to obtain
3.35,( 0 )4.31,( 0 )= 16.44. [RO-M+] = rnao/(mo + C) (14)
narrow-range ethoxylation when cesium or alkaline earths where C = miKeoc Consequently:
metals are used as catalysts. It must be concluded that
the type of cation in the catalyst influences the oligomer
distribution and is, therefore, involved in the reaction
mechanism. By considering the ability of polyethoxylated
surfactants to give crown ether complexes at low tem- It is thus possible to evaluate the concentration of each
perature, as described by Chan et al. (1970), Bailey et al. ionic couple by introducing the corresponding equilibrium
(19761, and Balasubramanian and Chandani (1983), it is constant Keoi.This must be done before each integration
reasonable to assume that, at the reaction temperature, step of the differential equations (7) and (81, and it allows
interactions between the ether groups and metal are still one to determine the evolution with time of all the involved
possible and affect above all the proton-transfer equilib- oligomers. For a correct solution of the described kinetic
rium. However, thiseffect is too weak, compared with that model, it is neceesary to know the ethylene oxide solubility
of anion nucleophilicity, at the reaction temperatures, to in the evolving reaction mixtures as well as the density of
influence also kinetic constants. Equilibrium 1becomes these mixtures.
When reaction rates are limited by mass transfer,
RO-M+ + RO(E0)iH s ROH + RO(EO);M+ (2) steady-state conditions for the ethylene oxide retention
and the equilibrium constant could be different from 1and can be assumed. Therefore, neglecting the initial transient
different for each oligomer. period and assuming the reaction is mainly occurring in
Therefore, the reaction scheme becomes the following the liquid bulk, we can write:
one: J = kLa([EO]i - [EO]b) =
[EO]bk([RO-M+]+ C[RO(EO);M+]] (16)
RO-M+ + EO 2RO(EOI1-M+ (3) i

Consequently
RO(EO)<M+ + EO A RO(E0I2-M+ (4)
k
RO(EO)n-l-M+ + EO 2.RO(EO);M+ (5)
with k l k2 = ... = k , k.
Equilibrium 1 can be written more generally as Rssults
A
RO(E0)jH + RO(EO)fM+ c-
Density Measurements. To correctly evaluate the
concentration of reagents, products, and catalyst, it is
RO(E0)jH + RO(EO);M+ (6) necessary to know the density of the evolving reaction
i=O,n j=O,n withizj mixture a t any reaction time. For this purpose, we mea-
sured the density of polyethoxylated mixtures character-
The following kinetic model can be written to interpret ized by different average molecular weights and at different
the kinetic runs temperatures. From results summarized in Figure 5, a
dmo/dt = -k[RO-M+][EO] (7) rough linear correlation is seen between density and tem-
perature, useful for interpolation or extrapolation.
dmi/dt = k[EO]{[RO(EO)i-<M+l- [RO(EO);M+ll (8) Solubility Measurements. Solubility measurements
where mo = [ROH] + [RO-M+],that is, the total concen- of ethylene oxide were performed, in the already decribed
tration of the substrate, while mi = [RO(EO),H] + [RO- way, for l-dodecanol and for polyethoxylated mixtures
(EO);M+] with i = 1, n. with different average numbers of adducts at different
Then, the equilibrium conditions must be considered: temperatures. The results are summarized in Table I in
the form of partition coefficients K = PEO/XEO.The
[RO(E0)jH] [RO(EO);M+] ethylene oxide solubility complies with Henry's law in all
Keji = (9) the considered cases. By plotting In K versus 103/T a
[RO(EO)jH] [RO(EO)j-M+]
linear trend is obtained, as can be seen in Figure 6.
and the overall catalyst concentration Ethylene oxide concentrations can be determined from the
partition coefficient with the relation
Bo = k[RO(EO);M+]
i=O
It is a rmmnable approximation to assume m0 ROH and
mi = [RO(EO);H]. Considering only the equilibria of the
- (10)
[EO] = -d 1
PM K(i)/PEO - 1 (18)
While the partition coefficient at a temperature different
2416 Ind. Eng. Chem. Res., Vol. 31, No. 11, 1992
In K ( i )
3, I

"
2.2 2.4 26 28 3

./
1 0 3 /(K)
~ 3
Figure 6. van't Hoff type plot for the Henry solubility constant of
ethylene oxide in 1-dodecanol and in ethoxylated dodecanol with 21
different average number of EO adducts. Number of adducts: ( 0 )
0,(0) 2.1, (A)4.3, ( 0 ) 14.5. 1

Table I. Solubility, at Different Temperatures, of Ethylene

00 / 20 40 60 80 103 120 140

Oxide in 1-Dodecanoland in Polyethoxylated 1-Dodecanol, Time (rnin)

with Different Averaue- Numbers of EO Adducts" Figure 7. Stimulation of ethylene oxide consumption during the
solvent T ("C) K(t) (atm) time for runs 1, 2, and 4.
1-dodecanol 70.0 4.67
99.0 6.90 tions, and ethylene oxide pressures, as shown in Table 11,
160.0 12.6 which summarizes the operative conditions of the runs
1-dodecanolethoxylated with 70.0 3.04 performed (1-5). For each of these runs the oligomer
2.1 mol of EO adducts 100.0 4.25 distributions at different reaction times also were deter-
150.0 7.43 mined. In the same table kinetic runs performed in a
1-dodecanolethoxylated with 70.0 1.87
4.3 mol of EO adducts 99.0 2.88 micropilot plant of Pressindustria type (6-10) are also
149.0 6.43 reported, where the ethylene oxide consumption rates were
1-dodecanolethoxylated with 70.0 3.56 measured together with residual fatty alcohol at a given
14.5 mol of EO adducts 100.0 5.66 final time. Still in the same table, the experimental con-
150.0 8.85 ditions of the runs performed by Satkowdci and Hsu (1957)
The measurements at each temperature have been performed (11-14) are reported. In this case, only the ethylene oxide
at different equilibrium pressures. The mean error in the partition consumption at different times was measured. All these
coefficient evaluation corresponds to about A5%. runs were simulated with the previously described model
and assuming, in each m e , that diffusional limitation is
from thoee reported in Table I can be determined with the negligible. In the case of the runs performed by us, this
following relation: fact was demonstrated by the observation that reaction
K ( i ) = K(1)(K(2)/K(1))[Tz/(T~-Tz)II(T~/T~)-~I
(19) rates were little affected by stirring rates.
In order to simulate all the mentioned kinetic runs, the
derived by Wilhelm and Battino (1973), provided that the kinetic and equilibrium parameters given in Table 11were
solution enthalpy can be assumed constant in the tem- used. As will be seen, only one equilibrium constant K,,
perature range considered. Solubility and kinetic param- = Keoiis needed in the case of KOH catalyst to reproduce
eters must always be considered together because evalu- well oligomer distributions. In Figure 7 the consumption
ation of kinetic parameters is strongly affected by ethylene of ethylene oxide, as a function of time, for the kinetic runs
oxide solubility. 1, 2, and 4 is reported. Points are experimental while
Kinetic Rune and Discuseion. Kinetic runs were curves are calculated data. In Figures 8, 9, and 10 ex-
performed at different temperatures, catalyst concentra- perimental and calculated distributions at different times
Table 11. List of the Kinetic Runs Considered with Both the Corresponding Operative Conditions and the Kinetic and
Equilibrium Parameters Applied for Simulation
run CI2 (mol) KOH (mol) PEO(atm) T ("'2) k (cm3mol-' E-') K W
1 0.896 0.0180 2.0 106.0 12.7 4.74
2 0.896 O.Oo90 2.0 128.0 38.5 4.73
3 0.896 O.Oo90 1.0 128.0 38.5 4.73
4 0.896 0.0184 2.0 100.0 9.2 4.78
5 0.896 0.0274 2.0 68.5 2.0 4.80
run LIAL123 CH30Na PEQ(atm) T ("C) k (cm3mol-' E-') K W
6 8.87 0.550 2.0 150.0 65.9 4.10
7 8.87 0.550 2.0 160.0 91.5 4.00
8 8.87 0.550 2.0 170.0 130.0 3.90
9 8.87 0.550 3.0 160.0 91.2 4.12
10 8.87 0.550 2.0 180.0 216.2 4.65
run C12 (mol) KOH (mol) PEO(atm) T ("'2) k (cm3mol-' 8-l) K W
11 1.0 0.036 1.4 107.5 10.9
12 1.0 0.036 1.4 137.5 48.3
13 1.0 0.036 1.4 167.5 135.1
14 1.0 0.036 1.4 197.5 253.7
 ili,
I 20

n-
Ind. Eng. Chem. b e . , Vol. 31, No. 11,1992 2417

0 4 8 0 4 8 0 4 8 0 2 4 6 8 10-12

tLLUL
Number of adducts
Figure 8. Simulation of the oligomer distribution at different reaction times in the case of run 1.
80

40
I
20
00 4

0 4 8 0 4 8 0 4 8 0 4 8
Number of adducts
Figure 9. Simulation of the oligomer distribution at different reaction times in the case of run 2.

0 4 8 0 4 8
L3
0- 4 8
Number of adducts
Figure 10. Simulation of the oligomer distribution at different reaction times in the case of run 4.

Table 111. Results Obtained in the Simulation of Runs 6-10 In K or In Keoi

Performed on the Pressindustria Tym Reactor
% residual EO consumption
alcohol mean rate (g/h)
run calcd exptl calcd exptl
6 26.9 26.8 4230 4230
7 26.1 25.8 5170 5170
8 25.7 25.5 6510 6510
9 26.9 27.2 8750 8700
10 28.9 29.8 9610 9620

Table IV. Results Obtained in the Simulation of the Runs

Performed by Satkowski and Heu (1967)
EO EO
consumption consumption
mean rate (g/h) mean rate (g/h)
run eXDtl calcd run emtl calcd 21 23 25 21 29
11 56.5 58.32 13 326.5 323.90 ~o~/T(K)
12 168.0 166.60 14 480.0 477.70 Figure 11. Arrheniua type plot for the kinetic constant and van’t
Hoff type plot for the equilibrium constant.
are reported, also for runs 1, 2, and 4, respectively.
Agreement is very satisfactory. related to the kinetic runs 6-10. Table IV shows resulta
For comparison purposes, Table I11 reports both ex- from the simulation of the Satkowski and Hsu rune
perimental and calculatedmean r a t a and residual alcohol, (11-14).
2418 Ind. Eng. Chem. Res., Vol. 31, No. 11, 1992
In Figure 11 all the kinetic and equilibrium parameters
obtained from the different kinetic runs are arranged in
an khenius-van't Hoff type plot. As can be seen, all the
runs considered show the same kinetic and equilibrium
parameters while the mass-transfer effect moderately ap-
pears only at higher temperature (>200 OC). The enthalpy
change corresponding to the equilibrium constant is quite
null and the equilibrium constant resulted about 4.8. The
kinetic parameters found are In A (cm3mol-' 8-9 = 20.3
f 0.30 and E = 13280 f 228 cal/mol.
Conclusions
We have confirmed that alkali-catalyzed fatty alcohol
ethoxylation occurs through an SN2 mechanism. Proton
exchange plays an important role in affecting both kinetics
and the oligomer distribution. Two main possibilities can
commonly be found (i) the substrate has acidic character,
as in the case of nonylphenol or fatty acids; (ii) the sub-
strate has the same acidic strength as the subsequent ad-
ducts. In the first case the equilibrium proton transfer is
completely dominated by the acidity of the substrate and
interaction of the anion with the metals can probably be
neglected. That is, in this case, we can write the equilib-
rium series
RXH + RXEiO- e RXEiOH + RX- i = 1,n (20)
with K,, = Ke2= Kei = K , being the acidity of the oli-
gomers of comparable strength. In this case the initiation
reaction may have a constant different from that of the
propagation reaction because the substrate is more acidic
than the ethoxylated chains. In the second case the in-
teraction of the ethoxylated chains with the cation may
influence the proton transfer and we can generally Write
RO-M+ + RO(E0)iH e ROH + RO(EO)[M+
i = 1, n (21)
by considering the possibility of different stabilities for the
ionic couples appearing in the reaction equilibrium (21).
In the case of fatty alcohol and KOH catalyst, only one
equilibrium constant is needed to reproduce the distri-
bution of oligomers. This constant is greater than 1despite
the acidity equivalence between the substrate and its ad-
ducts, and confii a greater stability of the ionic couples
containing ethoxylated anions. In the case of KOH the
chain length seems to have little or no influence on the
stability of the ionic couple.
Acknowledgment
Thanks are due to CNR, Progetto Finalizzato Chimica
Fine II,Enichem Augusta, and Pressindustria for financial
support.
Nomenclature
a = specific interface area, cm2/cm3
A = preexponential factor, cm3 mol-' s-l
Bo = catalyst concentration, equiv/cm3
d = density, g/cm3
E = activation energy, cal/mol
[EOIi = ethylene oxide interface concentration, mol/cm3
[EOIb= ethylene oxide bulk concentration, mol/cm3
J = mass-transfer rate, mol/(cm3-s)
k = kinetic constant, cm3 mol-' s-'
K,'i = equilibrium constant of proton-exchange reaction
Kh)= partition coefficient for ethylene oxide at temperature
Ti, atm
kL = gas-liquid mass-transfer coefficient, cm/s
mi = [ROEiH] + [ROE;M+], mol/cm3
mo = [ROH] + [RO-M+],mol/cm3
PEO= ethylene oxide partial pressure, atm
PM = molecular weight, g/mol
XEO= molar fraction of ethylene oxide
Registry No. HO(CHJI1CHB,112-53-8; ethylene oxide, 7521-8.
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Received for review June 30, 1992
Accepted July 9, 1992