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Adsorption of Ethoxylated Sulfonate and Nonionic Homologs on Coal

M. S. C E L I K 1
K. F. University of Petroleum & Minerals, KFUPM Box 785, Dhahran, 31261 Saudi Arabia
Received March 17, 1988; accepted July 6, 1988

The adsorption of ethoxylated sulfonates and nonionics of the same ethoxylation number on a low-
ash coal has been studied. The surfactant adsorption has been investigatedas a function of concentration,
pH, temperature, and ionic strength for three homologs. The zeta potential of the coal particles and the
surface tension of the supernatants have been concurrently determined to elucidate the orientation of
surfactant molecules on the coal surface as well as the mechanism of adsorption. The adsorption data
are utilized to calculatethermodynamic parameters such as the free energyof adsorption and the isoteric
heats of adsorption. 1989 Academic Press, Inc.

INTRODUCTION mechanism of adsorption as well as the m o d e


and configuration of the adsorbed surfactant
The adsorption properties of nonionic sur- molecules at the coal surface.
factants at the solid-liquid interface are im- EXPERIMENTAL
portant in a n u m b e r o f industrial processes Materials
such as flotation, flocculation, dispersion,
emulsification, and dewatering (1). Adsorption Buehler seam coal (0.13% ash by weight)
studies with nonionic surfactants on carbon in. in size from New Zealand was passed
have been extensively dealt with in the liter- through a roll crusher to obtain a + 100-mesh
ature (2). There is also an upsurge of interest fraction. The sub-100-mesh fraction was dis-
in the use of surfactants in coal technology carded to avoid any iron contamination. The
( 3 - 5 ) . However, fundamental aspects of the +100-mesh fraction was further ground in a
underlying p h e n o m e n a are still not well un- coffee grinder for 10 min. This coal sample
derstood due to the complexity of the coal was sealed in a plastic zipper bag and was kept
substance which incorporates a variety of in a freezer for subsequent use in adsorption
mineral constituents. Some recent studies have tests. The specific surface area of this coal by
utilized demineralized coals to investigate the BET technique using nitrogen adsorbate was
found to be 26.9 m2/g. Earlier surface area
effect of mineral matter on some properties of
coal ( 6 - 9 ) . There is, however, a need to use measurements (9) on the same coal by means
of air permeametry and BET technique re-
natural coals with low ash content in order to
vealed this particular coal to have insignificant
better understand the way nonionic surfac-
microporosity.
tants interact with coal.
The tributylphenol polyglycolethers
In this study, the adsorption, electrokinetic,
(C3xq~Ey) a n d e t h o x y l a t e d sulfonates
and surface tension properties of two series of
(Cax ~bEyS ) are products of Hoechst Chemical
nonionic surfactant and ethoxylated sulfonate
Co. For the sake of convenience these surfac-
homologs on a low-ash coal have been ex-
tants will be further abbreviated as E r and EyS,
amined. The data are analyzed to identify the
respectively. The symbols x, , y, and S re-
l Present address: Department of Mining and Minerals spectively denote the n u m b e r of CH2 groups
Engineering, Virginia Polytechnic Institute and State in the alkyl chain, the benzene ring, the n u m -
University, Blacksburg,VA 24061. ber of EO units in the polymer, and the anionic

428
0021-9797/89 $3.00
Copyright 1989 by Academic Press, Inc.
All rights of reproduction in any form reserved. Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
SURFACTANT ADSORPTION ON COAL 429

TABLE I

Thermodynamic Data for Coal/Surfactant System

Surfactant Surfaceexcess(F) CMC Area per molecule AG~t~ AG~i~ AH~t~


designation (mole/m2) (kmole/m3) (A2) (kcal/mole) (kcal/mole) (kcal/mole)

a
E13 2.01 X 10-7 1.0 X 10-4 719 -6.72 -5.40
Ej5 1.56 X 10-7 1.2 10-4 1278 -6.85 -5.22 -0.90
El8 1.00 X 10-7 1.6 X 10-4 1941 --7.09 --5.11

EloS 2.31 X 10-7 1.1 X 10-4 826 --6.66 --5.46


E15S 1.30 X 10-7 1.5 X 10-4 1065 --6.95 --5.35 -0.79
EIsS 8.56 X 10-8 1.8 X 10-4 1661 -7.17 -5.18

C4H 9 C4H 9

C 4 H 9 - ~ O - - (CH2. CH2. O)y H C 4 H 9 ~ O - - (CH 2"CH 2" O)y SO3Na+

C4H9 C4H 9

sulfonate group. Some of the properties of made on particles over a micrometer in size
these surfactants are listed in Table I. Sodium in order to keep the ratio of particle radius of
dodecylbenzenesulfonate (NaDDBS) of 85% curvature to electrical double-layer thickness
purity was purchased from Pfaltz & Bauer. All large. The samples were taken from the actual
the solutions were prepared using distilled and supernatants following the adsorption tests.
deionized water. About 22 ml of a clear supernatant was re-
moved from the adsorption test vial and in-
Methods troduced into a Pyrex electrophoresis cell. An
The adsorption experiments were con- appropriate amount of coal particles was pi-
ducted in 35-ml sealed screw-cap Teflon vials. petted out of the coal bed and placed in the
Thirty milliliters of a surfactant solution of cell. This procedure assured elimination of
known concentration having 2 10 -3 kmole/ very fine coal particles which produced a black
m 3 NaC1 was introduced into a vial containing color and worsened the visibility of coal par-
0.3 g of coal sample. The samples were con- ticles.
ditioned in a constant temperature shaking The critical micelle concentration (CMC)
water bath for 6 h, centrifuged, and then kept of all surfactants was determined by means of
undisturbed at the same temperature for an the surface tension technique. A Kruss digital
additional 6 h. This procedure was necessary tensiometer with the ring method was utilized.
to eliminate the perturbations caused during The CMC was determined in the presence of
centrifugation at a lower temperature. The 2 X 10 -3 k m o l e / m 3 NaC1 for both the pure
equilibrium concentration ofsurfactant in the surfactants and the actual supernatants fop
supernatant was determined spectrophoto- lowing the adsorption tests. All surface tension
metrically from the optical density at 276 nm. measurements were carried out at 25C.
The amount adsorbed was calculated from the
difference between the initial and final con- RESULTS AND DISCUSSION
centrations.
CMC Measurements
The zeta potential measurements were per-
formed by a Zeta Meter 3.0 equipped with a The CMC values for both Ey and EyS ho-
microprocessor unit. The measurements were mologs are plotted in Fig. 1 as a function of
Journal of ColloM and Interface Science, Vol. 129,No. 2, May 1989
430 M.S. CELIK

3xlff ~
2XlO-3kmol/m3 NaCI
T- 25 C

2xiC A o EyS
Ey

t~E

ixio-4

6Xlff 5 I, I I I I
10 12 14 16 18
EO NUMBER ( y )

FIG. l. CMCdependenceofnonionicsand ethoxylatedsulfonatesvs EOnumber.

the ethoxylation (EO) number. It is evident (8, 13, 14). However, in the presence of 4
that the CMC values for the two series yielded X 10 -4 kmole/m 3 of nonionic surfactant
straight lines on a semilog plot with slightly comprising different EO numbers, an inter-
different slopes. The ethoxylated sulfonates esting observation was made in that the iep of
produced higher CMCs than the nonionics of all surfactants shifted about 2.2 units toward
the same EO number; this behavior is consis- the alkaline pH. A similar observation was also
tent with the respective surface activity of each made previously with polyoxyethylene non-
class of surfactant. The presence of the sul- ylphenol homologs (9).
fonate group in the ethoxylated sulfonate op- This observation can be ascribed to a shift
poses micellization and in turn results in either of iep or of the shear plane (15). Ad-
higher CMCs~ The CMC values are generally sorption of nonionic surfactants on coal at low
in agreement with the reported literature val- coverages is believed to occur through the hy-
ues for similar surfactants (10-11). It should drocarbon part of the molecule lying flat on
be noted that the CMC values obtained from the hydrophobic surface (2). If the adsorption
the actual supernatants were slightly higher for energy of the surfactant is greater than that of
all surfactants tested. Similarly, the surface the water molecules, displacement of some of
tension measurements on the actual super- the water dipoles will lead to a change in the
natants gave higher values by up to 1 m N / m Stern potential due to decreased dipolar in-
than those on pure solutions, probably due to teractions. Mechanical displacement of the
release of ions and organic humic acid-like shear plane, on the other hand, can result due
substances from the coal matrix (12). to adsorbed bulky surfactant molecules being
projected some distance beyond the original
shear plane (15).
Zeta Potential Measurements In the present system, the nonionic surfac-
The results of zeta potential measurements tant, irrespective of its EO number, produces
vs pH for the two series of surfactants are pre- the same shift of the shear plane as illustrated
sented in Figs. 2 and 3. In the absence of any in Fig. 2. This can be explained by the fact
surfactant the coal exhibited an isoelectric that the water molecules are displaced by the
point (iep) of approximately 5, which falls hydrocarbon chain alone and the contribution
within the iep values reported in the literature of the EO chain is minimal. Since the nonionic
Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
SURFACTANT ADSORPTION ON COAL 431

+60

0 NO SURFACTANT
o El3
+40 E15
El8

+20
>
E

I
12
o pH

-20
COAL/4XIO-4 k~l/m 3 EY ~ a

2X]O-3 kmol/m3 NaCI X


-40
T= 25C 0"~

-60

FIG, 2. Variation of zeta potential of coal with pH in the absence and presence of surfactant.

chain itself does not contribute to any free molecules by the alkyl chain followed by a de-
changes in the electrical double layer, the ad- crease in dipolar interactions is responsible for
sorbed molecules reduce the surface charge the observed shift in Stern potential. Mechan-
only by covering the adsorbed sites on both ical displacement is unlikely as it would induce
sides of the iep. Consequently, the reduced zeta different shifts with increased EO chain length.
potential vs pH curves exhibited symmetry Figure 3 presents the zeta potential vs pH
with respect to the iep. The results presented data obtained with ethoxylated sulfonates of
above reveal that displacement of the water varying EO number. Included in the data is

-50

-40
0 0 o
'0 ,0 0 v
Lt, & W
& La
, -30 COAL/4XlO-4kmol/m3 E S
Y
2X10-3krm)l/m3 NaCI
T= 25 C
-20

0 E18S
oE S
15
-10 t, EIoS
NaDDBS

| i t I i i

2 4 6 8 10 12 14
pH

FIG. 3. Zeta potential of coal in the presence of ethoxylated sulfonates and NaDDBS.
Journal of Colloid and Interface Science, Vol. 129, No, 2, May 1989
432 M.S. CELIK

NaDDBS with a linear hydrocarbon chain. Similarly, NaDDBS, which is devoid of EO


Unlike nonionics, ethoxylated sulfonates units, showed that coal is equally receptive to
demonstrated constant negative zeta potentials nonpolar chains irrespective of its charge.
in the entire pH range tested. Slight increases NaDDBS produced higher negative zeta po-
in the negative zeta potentials with increases tential values than the ethoxylated sulfonates.
in the EO number seem to be contrary to the Processes governed by physical adsorption
data on magnitude of adsorption (see Fig. 5 ). usually involve electrostatic interactions. For
This anomaly can be ascribed to the increasing instance, adsorption of amine on oxidized coal
equilibrium pH values found upon increasing is reported to occur through electrostatic at-
the EO number. For instance, the equilibrium traction (16). Also, Bisio et al. (17) report
pH values for the nonionic surfactants were electrostatic interaction of cationic surfactant
approximately 7.5, 8.0, and 9.0, respectively. with a negatively charged hydrophobic mem-
Although increasing pH in the range 7.5 to 9.0 brane near and above the CMC. It is to be
does not affect the adsorption capacity of the noted that coal contains, in addition to surface
surfactant, it concurrently increases the zeta functional groups, some mineral matter which
potentials. Interestingly, the ethoxylated sul- imparts a certain degree of charged groups to
fonates did not exhibit an iep shift similar to coal. However, the low-ash coal used in this
that observed in the case of nonionics of the study supports the contention that the ad-
same structure and EO number. This finding sorption is not augmented by electrostatic in-
clearly reveals the role of charged sulfonate teractions between the oppositely charged
groups in controlling the double-layer prop- species.
erties. The zeta potential results further dem- Effect of pH on Adsorption
onstrate that the hydrocarbon part of the sur-
factant molecule has equal affinity to the coal The dependence on pH of the adsorption
surface both below and above the iep. of Ey and EyS homologs onto coal at a con-

2.4 0
EIoS o o o

2.0 E13 m ,,

c,J

"~ 1.6
q5 "." "- ; L ~
r.. E15S ~ ~ ~ A .
o
vx 1.2
~a

N E18S O o o 0

COAL/4XIO-4kmol/m3 SURFACTANT

~: 0.4 2X10-3 kmol/m3 NaCl, T= 25 C

i I i i i i
2 4 6 8 i0 12 14
pH

FIG. 4. Adsorption of various surfactants on coal as a function of pH.

Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
S U R F A C T A N T A D S O R P T I O N ON COAL 433

stant initial surfactant concentration is illus- Mechanism of Surfactant Adsorption


trated in Fig. 4. While the adsorption remained on Coal
constant in the acidic and neutral pH regions,
it showed a gradual decrease in the alkaline The adsorption of ethoxylated sulfonate and
region above approximately pH 9. Insensitiv- nonionic homologs onto coal is presented in
ity of adsorption to pH has been reported for Fig. 5, where adsorption density is plotted vs
coal/o-cresol, terpineol, MIBC (6) and also the equilibrium concentration. Langmuir-type
for coal/dextrin (7) and coal/nonionics sys- isotherms with the plateau region occurring at
tems (9). This insensitivity of adsorption to or below CMC were generally obtained. The
pH was utilized by performing the experiments CMC values indicated by arrows were ob-
at the natural pH (6.8-9.0). tained using the actual Supernatants.
Coal is known to acquire gradual hydro- Nonionic surfactants are known to adsorb
philicity above about pH 6 and complete hy- physically on both polar and nonpolar sub-
drophilicity above pH 10 due to the formation strates (4, 5, 15, 17, 19-26). Adsorption of
either of surface functional groups (8) or of nonionic surfactants on hydrophobic solids
hydroxy complexes of multivalent ions on coal such as coal usually undergoes three or four
surfaces (18). Insensitivity of adsorption to pH stages depending on the nature of adsorbent
over a wide range reveals that adsorption oc- and adsorbate. The nonpolar portion of the
curs predominantly through hydrophobic in- molecule, in the first stage, adsorbs on coal via
teractions. van der Waals interactions and displaces the

3.0

2.5
CMC o o EIoS
0 u 0 0

~S" 2.0
0E13

i.5

1.0

COAL/SURFACTANT

0,5 2X10" 3 kmol/m 3 NaCi


T = 25 C , pH= 6 . 8 - 9 . 0 ( N a t u r a l )

i i I i i i L
4 8 12 16 20 24 28 32

EQUILIBRIUM CONCENTRATION(CX 105), kmol/m 3

FIG. 5. Adsorption of nonionics and ethoxylated sulfonates on coal.

Journal of Colloid and Interface Science, Vol. 129, No. 2. May 1989
434 M.S. CELIK

weakly adsorbed water molecules from the solvent molecules should be of the same size.
surface. In the second stage, the surface which However, it has been shown that these two
is almost free of water molecules achieves a conditions are mutually compensating terms,
monolayer coverage. The third stage is dom- resulting in a good Langmuir fit (28). The ad-
inated by lateral interactions of the surfactant sorption isotherms in Fig. 5 were found to ap-
molecules which lead to only a marginal in- proximately obey a Langmuir-type expression,
crease in adsorption. Formation of hemimi- Y CK
celles on the surface beyond the CMC (24) or O . . . . [1]
existence of a planar monolayer has been pro-
Fm 1 + CK '

posed to account for the observations regard- where O is the surface coverage, I'm is the
ing the fourth stage (2). Data from hydrody- maximum amount adsorbed, C is the equilib-
namic layer thickness measurements on poly- rium concentration of the adsorbate in the
carbonate membrane indicate that nonionics bulk, and P is the amount adsorbed at con-
adsorb horizontally below the CMC, become centration C. The equilibrium constant K is
vertical near the CMC, and form a bilayer a measure of the partitioning of the surfactant
above the CMC (17). Electrokinetic measure- and water between the surface and bulk so-
ments also confirm the above inference (27). lution and is related to the apparent adsorption
As shown in Fig. 5, the saturation adsorp- free energy (AGads) as
tion values decreased with increases in the EO
AGads = - R T In K, [2]
number. Table I presents the calculated cross-
sectional areas of the adsorbate molecules for where R and T are the gas constant and ab-
each EO number. The marked increase in cal- solute temperature, respectively. Langmuir
culated areas per adsorbate molecule, ranging plots of 1/ I' vs 1/ C yielded a straight line with
from 719 to 1941 A2, suggests that the EO a slope equal to 1am and intercept at K. The
chain also extends in a fiat configuration along adsorption free energies calculated using Eq.
with the alkyl-aryl hydrophobe. If adsorption [2] are presented in Table I as a function of
occurred only through vertical orientation of the EO number for both Ey and EyS homologs.
the alkyl-aryl moiety, the cross-sectional areas As the molecule is lying flat on the surface,
would have been independent of the EO num- the adsorption energy should increase by a
ber. The cross-sectional areas for the n-alkyl certain increment for each additional CH2 or
chain (C4H9), benzene ring, EO chain (El0), EO group. The magnitude of adsorption free
and sulfonate group are 26, 25, 145, and 30 energy varies between 6.66 and 7.17 kcal/mole
A2, respectively. The large values for the cal- for EyS homologs and between 6.72 and 7.09
culated areas indicate that both nonionics and kcal/mole for Ey homologs. Since both series
ethoxylated sulfonates are indeed adsorbing of surfactants yield approximately the same
through their alkyl-aryl hydrophobes' lying magnitude of adsorption free energy, it sug-
fiat on the coal surface. The EO chain is either gests that the adsorption involves hydrophobic
weakly adsorbed or free and should be pro- bonding only. The free energies of adsorption
jected away from the interface with an angle of terpineol, cresol, dextrin, and phenol on
dictated by the ratio of adsorption and hydra- coal have been reported as -9.7, -8.2, -8.0,
tion forces. The large cross-sectional areas and -5.5 kcal/mole, respectively (6, 29). The
suggest that the EO chain has a low angle of standard decrease in the free energy of ad-
deflection. sorption per EO group was found to be ap-
The adsorption of nonionic surfactants on proximately 70 cal/mole as shown in Fig. 6.
coal can be described in terms of a Langmuir- The value of 102 T- 60 cal/mole obtained by
type equation although two of the conditions Klimenko et al. ( 3 0 ) for the activated carbon/
are not met: (i) there should be no adsorbate- nonionics system is in agreement with the
solvent interactions; (ii) the adsorbate and above data.
Journal of Colloid and Interface Science, Vot. 129, No. 2, May 1989
S U R F A C T A N T A D S O R P T I O N O N COAL 435

-7.2
EyS

-7.1 Ey

-7.(
?.

%o
-6.~

-6.

-6.d 8 I0 1 14 16 18 20
EO NUMBER

FIG. 6. Effect of EO number on adsorption free energy for coal/surfactant system.

Kronberg et al. (3 I) have shown that with energy is due to the replacement of surface-
nonpolar adsorbents, the adsorption energy is water contacts by surface-hydrophobic moiety
close to the micellization energy. As most contacts; this effect is dependent only on the
nonpolar adsorbents show similar adsorption nature of the adsorbent (32).
free energies, the solution properties of the The zeta potential data corresponding to the
surfactant should be a driving force for ad- adsorption isotherms given in Fig. 7 generally
sorption. This can be determined by calculat- followed a particular trend for different EO
ing the free energies of micellization for the numbers. While the nonionics exhibited a
surfactant using sharper decrease in zeta potentials up to the
o CMC, the ethoxylated sulfonates showed a
AGmic = R T In XcMc. [3]
marginal decrease below the CMC. Both sys-
The calculated free energies of micellization tems yielded almost constant potentials above
given in Table I demonstrate that about 70 to approximately the CMC. Since ethoxylated
80% of the adsorption free energy is due to sulfonates have negative sulfonate groups
nonspecific factors such as orientation of the projecting toward the solution, their zeta po-
surfactant molecules at the coal surface. This tentials are more negative than those of the
orientation of the surfactant molecule through nonionics. Also, the zeta potentials become
contact of its hydrophobic moiety with the slightly more negative with increases in the
surface and projection of the hydrophilic part EO number for both series due to the mag-
toward the solution necessitates replacement nitude of adsorption being higher with the
ofwater-hydrophobic contacts by surfactant- lower EO numbers.
surfactant contacts between the hydrophobic
portions of the surfactant (31). This effect is Dependence of Adsorption on Temperature
influenced only by the nature of the surfactant.
In the case of nonionics and ethoxylated sul- The effect of temperature on the adsorption
fonates about 20 to 30% of the adsorption free of nonionic surfactant (El 5) and ethoxylated
Journal of Colloid and Interface Science, VoI. 129, No, 2, May 1989
436 M.S. CELIK

-40
~ ~ o o 9 O E18S
o ~ EI5S
EIoS
-30

-20

ao ~-o E18
-10 COAL/4XIO
-4 k m o ~ E15
2X10-3kmol/m3 NaCl, T=25C E13

.0 I I
10-5 10-4 10-3 10-2
INITIALSURFACTANTCONCENTRATO
I N,kmol/m3
FIG. 7. Zeta potential of coal vs initial surfactant concentration for various surfactants.

sulfonate (E~5S) is illustrated in Fig. 8 at three factant molecule becomes more hydrophobic
levels of temperature. The adsorption process with increased temperature due to gradual
can again be described by the Langmuir equa- dissolvafion of the EO chain which dominates
tion. However, the adsorption exhibited dras- the properties of the surfactant molecule more
tic changes with increased temperature, par- than the polar sulfonate head. Therefore, the
ticularly for the nonionic surfactant. Such re- increase obtained in saturation adsorption
sults have also been reported in the literature values with ethoxylated sulfonates showed a
(2, 9, 25). Increasing the temperature gener- lower temperature dependence than that ob-
ally reduces the solubility with a concomitant tained with the nonionics.
increase in the surface activity of a nonionic The temperature dependence of adsorption
surfactant. Surfactant-solvent interactions can be utilized to calculate the isoteric heat of
with nonionics are highly temperature-sensi- adsorption for the interaction of the nonionic
tive. Surfactant molecules acquire increased surfactant with the coal surface using the
hydrophobicity upon gradual dissolvation of Clausius-Clapeyron equation in the form
the EO chain (32). This results not only in
din K AH
more compact molecular structure but also in
d(I/T) R ' [4]
enhanced surface activity accompanying
higher saturation adsorption values. The data where K is the equilibrium constant obtained
on the adsorption of nonionic surfactant given from the Langmulr plots and M-/is the isoteric
in Fig. 8 clearly illustrate the sensitivity ofsur- heat of adsorption. The slope of In K vs 1/ T
factant to temperature. plots given in Fig. 9 can be used to calculate
Unlike nonionics, anionic surfactants are AH for El 5and E15S. The thermodynamic data
less affected by temperature. Increasing the tabulated in Table I yielded isoteric heats of
temperature increases the solubility and hence -0.90 and -0.79 kcal/mole for E15 and E~sS,
the CMC with a concomitant decrease in the respectively. The heats of adsorption are ap-
surface activity of an anionic surfactant. But parently small and decrease with the addition
in the case of ethoxylated sulfonate, the sur- of the sulfonate group. It should be noted that
Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
SURFACTANT ADSORPTION ON COAL 437

COAL/SURFACTANT
2XlO-3kmol/m 3 NaCI

71- zx
c~lE

E15 75 C
E15S 75 C
0 E15 50 C
o 50 C
E15S
0 E15 25 C
EIbS 25 C

3F& / ~ u

0 0

Q
0 4 8 12 16 20 24 28 32
EQUILIBRIUM CONCENTRATION(CXI05), kmol/m3

F I G . 8. Effect o f t e m p e r a t u r e on adsorption ofdifferent surfactants o n t o coal.

the use of the Clausius-Clapeyron equation to Effect of Ionic Strength


obtain heats of adsorption from adsorption
isotherms has been a subject of criticism (22- Results for the adsorption of E15 and E15S
23) because the interfacial excess inherent in onto coal at two different ionic strengths are
Eq. [4] is assumed to be independent of tem- presented in Fig. 10. The changes in ionic
perature. However, Haung et al. (29) found strength can generally affect surfactant ad-
good agreement between the experimentally sorption due to (i) compression of the elec-
measured calorimetric data and the isoteric trical double layer around the coal surface, (ii)
heats of adsorption obtained by means of the the increase in the effective concentration of
Clausius-Clapeyron equation. The small iso- surfactant around the coal surface owing to
teric heats of adsorption values suggest that the salting-out effect, (iii) lowering of the cloud
these surfactants adsorb on coal primarily via point of the nonionic surfactant, and (iv) en-
van der Waals and entropy-driven hydropho- hanced micellization and consequent reduc-
bic binding. tion in CMC.
Journal of Colloid and Interface Science, Vol. 129, No. 2, May 1989
438 M.S. CELIK

11.8
o

11.6

11.4

11.2

I i .0
o

10.8

10.6
2.8 2 9 3 0 3.1 3.2 3.3 3.4
I0-3/T

FIG. 9. Plots to determine isoteric heats of adsorption for coal/surfactant system.

The increase in adsorption observed in the 2. The adsorption of nonionic surfactants


case of nonionic surfactant can be attributed and ethoxylated sulfonates on the coal follows
to the mechanisms listed above except (i). On the Langmuir-type isotherm. Increasing the
the other hand, lateral interactions between EO number reduces the surfactant adsorption
the sulfonate heads of the ethoxylated sulfo- on the coal. The homologs of both surfactants
nate oppose adsorption and miceUization, adsorb primarily via the alkyl-aryl hydro-
whereas salting-out and cloud point lowering phobe's lying flat on the coal surface. The EO
enhance adsorption. It is the net effect of these chain and/or sulfonate group is projected to-
two opposing forces that determines the mag- ward the aqueous phase. Interestingly, the ad-
nitude of adsorption. In the present case, the sorption of ethoxylated sulfonate is not aug-
net effect seems to be marginal. Therefore, the mented by the presence of the sulfonate group.
effect of ionic strength on adsorption is more This reveals the negligible effect of electrostatic
pronounced with the nonionic surfactant. interactions between the oppositely charged
species and low-ash coal.
CONCLUSIONS 3. The free energy of adsorption varied be-
tween 6.66 and 7.17 kcal/mole for the ethox-
1. While the nonionic surfactants shifted ylated sulfonates and between 6.72 and 7.09
the iep of the coal from 5 to 7.2, the coal par- kcal/mole for the nonionic surfactants. The
ticles in the presence of ethoxylated sulfonates standard decrease in the free energy of ad-
exhibited constant zeta potentials in the entire sorption is found to be approximately 70 cal/
pH range tested. The iep shift observed with mole per EO group. While 70 to 80% of the
the nonionics is attributed to the displacement adsorption free energy is due to orientation of
of water molecules by the alkyl chain followed surfactant molecules at the coal surface, 20 to
by a decrease in dipolar interactions. 30% of it accounts for the replacement of sur-

Journal of Colloid and lnterface Science, Vol. 129, No. 2, May 1989
SURFACTANT ADSORPTION ON COAL 439

12

10

n
~" 0 (-;'

8
o E15 , 2X10 - I kmol/m 3 NaCI
o El5 , 2X10 -3 kmol/m 3 NaCI
x
E15 S , 2XIO - I kmol/m 3 NaCI
6
E15 S , 2X10 -3 kmol/m 3 NaCI

4
cz,
o COAL/SURFACTANT
T= 75 C
2

0 O 4 8, 112 ~6 20, ,
24 2'8 ' 32
EQUILIBRIUM CONCENTRATION(CXIO 5) , kmol/m 3

FIG. 10. Effect of ionic strength on surfactant adsorption onto coal.

face-water contacts by surface-hydrophobic 4. Aston, J. R., Deacon, M. J., Furlong, D. N., Healy,
T. W., and Lau, A. C.-M., in "Proceedings of the
m o i e t y contacts.
First Australian Coal Preparation Conference"
4. T h e isoteric h e a t s o f a d s o r p t i o n calcu- (A. R. Swanson, Ed.), p. 358, Newey and Beath,
lated b y m e a n s o f t h e C l a u s i u s - C l a p e y r o n 1981.
e q u a t i o n are s m a l l ( - 0 . 7 9 a n d - 0 . 9 0 k c a l / 5. Aston, J. R., Drummond, C. J., Scales, P. J., and
m o l e for t h e e t h o x y l a t e d s u l f o n a t e a n d n o n - Healy, T. W., in "Proceedings of the Second Aus-
ionic surfactant, respectively), indicating that tralian Coal Preparation Conference" (R. L.
Whitmore, Ed.), p. 148. Westminster Press, Phil-
the a d s o r p t i o n is m a i n l y g o v e r n e d b y e n t r o p y -
adelphia, 1983.
driven hydrophobic bonding. 6. Fuerstenau, D. W., and Pradip, Colloids Surf 4, 229
(1982).
ACKNOWLEDGMENTS 7. Miller, J. D., Lin, C. L., and Chang, S. S., Colloids
Surf. 8, 351 (1983).
The author is grateful to Dr. R.-H. Yoon for providing 8. Fuerstenau, D. W., Rosenbaum, J. M., and Laskowski,
the coal sample and to the Hoechst Chemical Co. for sup- J., Colloids Surf 8, 153 (1983).
plying the surfaetant samples. 9. Celik, M. S., and Yoon, R-H., "Adsorption of Non-
ionic Surfactants on Coal," presented at ACS Na-
tional Meeting, New York, 1986.
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Journalof ColloidandInterfaceScience,Vol.129,No. 2, May 1989