CROATICA CHEMICA ACTA CCACAA 52 (2) 67-86 (1979)

YU ISSN 0011-1643
CCA-1145 541.18:3
Conference Paper;
Author's Review

Physico-Chemical Aspects of Adsorption of Surface Active

Agents on Minerals*
P. Somasundaran
Henry Krumb School of Mines, Colv/mbia University, New York, New York, 10027, USA
Received December 18, 1978

Ba sic principles and some special aspects of adsorption on

minerals are discussed. Electrostatic forces, lateral interaction be-
tween surfactants, chemical and other forces are discussed in more
detail as well as the role of the chemical state of surfactants. It is
pointed out the importance of pretreatment of mineral systems
which can affect their electrokinetic behaviour as well as the pre-
sence of other charged particles in solution if electrostatic forces
play a major role. The sharp increase in electrophoretic mobility at
a given adsorbtion density for certain conditions and appearance
of maximum flotation of certain minerals with hydrolyzable sur-
. factants a t the point of zero charge are attributed to micellisation
and covalent bonding respectively with possible polymer formation.
Other factors such as hydrogen bonding, solvation or desol-
vation of species and hydrophobic bonding are mentioned. Special
attention is paid to the adsorption in micellar solutions and ad-
sorption kinetics.
INTRODUCTION

Adsorption of surfactants on particulates is a governing parameter in a

number of interfacial processes such as flotation, detergency, tertiary oil re-
covery using surfactant flooding , lubrication, flocculation and clarification for
waste treatment, comminution, chromatography etc. Process of adsorption is
in turn determined by a large number of system variables such as chemical
and structural properties of the particulate including solubility and interfacial
electrochemical potential, chemical and physical properties of solution such
as salinity, pH and temperature and even the chemical make-up of the
adsorbent, particularly in terms of purity. Considerable advance has been
made in the past in developing an understanding of the role of various system
properties. This has been covered in several recent reviews (Somasundaran
and Grieves, 1975; Goddard and Somasundaran, 1976; Somasundaran and Hanna,
1977, Mittal, 1975, Fuerstenau, 1971, Healy, 1974). Here we will examine some
special aspects of adsorption on minerals.
* Presented at the 4'" Yugoslav Symposium on Surface Active Substances, held
in Dubrovnik, Croatia, Yugoslavia, October 17-21, 1977.
68 P . SOMASUNDARAN

BASIC PRINCIPLES

Adsorption of any species in an interfacial region is the result of favorable

chemical or physical interaction between the adsorbate species and either the
adsorbent surface species or other intermediary species that accumulate in the
interfacial region. If i1G0 bi is the free energy term corresponding to transfer of
the adsorbent species from the bulk (b) to the interfacial region (i) , concentration
in the interfacial region, c;, can be expressed as

(1)

whereas ch is the bulk concentration in mol dm-3, R is the gas constant and T
is the absolute temperature.
To express the adsorption in terms of mol/cm 2 we simply multiply the
right-hand side of equation by the thickness of the adsorbed layer, i .

-l';GOads
I' i = T cb exp RT (2)

.:1G0adS> is equal to .:1G 0b; and can be the result of electrostatic attraction, covalent
bonding, hydrogen bonding or non-polar bonding between the adsorbate and
adsorbent species, lateral interaction between the adsorbed species etc. In
addition, desolvation or solvation of any species due to the adsorption process
can also contribute towards determining the exti=nt of adsorption. Another
factor that is usually ignored arises from the variations in such physical
properties as structure and dielectric constant of the medium from the bulk
to interfacial region. Lack of precise information on the above variations makes
treatment of adsorption mechanisms difficult. One or more of the above
factors can play a governing role in adsorption depending on the mineral-
-solution system. In fact , some of the factors can even oppose adsorption
(positive 11G), but all that is needed for adsorption to take place is the total
sum i1G 0ads to be negative. One other point to note is that even if i1G 0ads under
equilibrium conditions is positive, species can remain adsorbed on a solid if
i1G 0ads is negative at some point in time prior to attainment of equilibrium and
if adsoption is irreversible.
Our work in recent years has been aimed towards establishing the role
of some of the major factors in determining adsorption in various systems.

Electrostatic Adsorption
Particulates are often charged in solution either due to preferential dis-
solution of species, hydrolysis of surface species or even adsorption of various
charged ions and complexes. On such particulates, adsorption of species that
are charged oppositely can take place with a free energy of adsorption, i1G0elec•
given by ZF1.fJ;, Z being valency of the adsorbate species, F the Faraday
constant and 'l.jJ; the interfacial potential. The role of electrostatic forces is
clearly illustrated in Figure 1 where adsorption of dodecylsulfonate on alumina
is plotted as a function of pH at a constant equilibrium bulk sulfonate con-
centration of 3 X 10- 5 mol dm- 3 . The point of zero charge of this alumina is at
 PHYSICO-CHEMICAL ASPECTS OF ADSORPTION
69

10 0
MONOLAYER7
I
------------ - -------------T-
I
[Nac
12
so3J = 3x10-5mol dm-3:

f:J
I = 2x10-3mol dm-3:
I +1 -
'E 1.0 I I
I "'
I
I
0

-
E
I >
<l: I
~
z'
-1
+21
CD
>- :21 '
::>I ;2
t:
CJ)
_JI
<!I
z 0.1 ~
I
w LL I +3
0 o, _J
z u'
NI CD
0 0
o._I
i= I :2
0..
0:
I +4u
0 I i=
I
CJ)
I
w
00.01 I a::
<l: I
0
I
I
I +5 25
I a::
I I-
I u
I w
_J
I
I w
0.0012 +6
3 4 5 6 7 8 9
pH

Figure 1. Adsorption of dodecylsulfonate on alumina as function of pH (Somasundaran and

Fuerstenau, 1966).

pH = 9.1. It is then to be noted that only below pH = 9.1, when the alumina is
positively charged, does the anionic ·sulfonate adsorb in significant amounts
(Somasundaran and Fuerstenau, 1966). We have obtained similar correlation
for adsorption of sulfonate and amine on calcite (Somasundaran and Agar,
1967). The results obtained for mineral systems do not however often produce
such correlations since the values obtained are affected by the pretreatment
procedures used (Somasundaran, 1972, Kulkarni and Somasundaran, 1977, So-
masundaran, 1970). We have examined the effects of various commonly used
pretreatments such as desliming, ultrasonic scrubbing and leaching with dilute
nitric, hydrofluoric and sodium hydroxide solutions on the electrokinetic
properties of quartz in aqueous solutions. It was found that these treatments
can affect, sometimes severely, the electrokinetic properties of quartz. The
changes in these properties even during subsequent aging is found to be
governed by the type of treatment used. For example, the isoeiectric point of
quartz can be raised from below 2 to as high as 6 by leaching it in hydrofluoric
solution (See Figure 2). Upon ageing the hydrofluoric acid leached quartz in
water, the isoelectric point slowly shifts to lower values over a period of
several days.
In systems where electrostatic forces play a major role, presence of other
charged species in solution can influence adsorption owing to competition for
adsorption sites by ions that are charged similarly to the adsorbate species.
70 P. SOMASUNDARAN

Thus flotation of quartz using amine is found to be depressed by the addition

of potassium nitrate owing to the reduction of adsorption of dodecylammonium
ions on quartz by the competing potassium ions (See Figure 3) (Somasundaran,
-so.--~~.-~~.-~~-.---,.~-.-~~--.

I
I tc= 35 °C

I I= 10-3 mol dm-3

I
I 022 h AGING
>
E I r6h
I f
I
J
...J 0 4 h
<(
f-
z
~ 0
_!_ __
0
CL
<(
f-
w
N

40

2 4 6 8 10
pH
Figure 2. Zeta potential of quartz t rea te d w ith HF and the n w ith hot NaOH solutions as a
function of pH without a ging , and a t pH = 6 a fter 4, 6, and 22 hou rs of aging ; dotted curve is
for equilibrium values obtained for HNO,i-tr e ated quartz for comparison (Kulkarni and Soma-
sundara n, 1977).

80
A

0 60
w
!;i
0
iZ40 A
[DDA)=1 .5xl0- 4 mo t dm-3 A A

QUARTZ
20 pHz 5.8
A

0
16 5 104 16 3 10- 2 10-1
KN0 3 CONCENTRATION /(mol dm-3)
Figure 3. Flotation of quartz as a function of KNO, concentrat ion at natural pH of 5.8 in
1.5 X 10-• mot dm-s dode c y l-ammonium aceta te solutions (Somasundaran, 1974).
 PHYSICO -CHEMICAL ASPECTS OF ADSORPTION 71

1974). Effectively, addition of the potassium ions causes a compression of the

electrical double layer and reduces interfacial potential that is responsible for
the adsorption of the dodecylammonium ions. In contrast to the above, uptake
of ions that are charged oppositely to the surfactant can produce an increase on
adsorption of it provided the surface is not already fully charged. It is interesting
to note in this regard the observation of Saleeb and Hanna (Saleeb and Hanna,
1969; Hanna, 1976) that the introduction of SQ 4 2- ions increased the adsorption of
a cationic surfactant, cetyltrimethylammonium bromide, on CaC0 3 , but not
on Ca,(PO,L. This was attributed to the possible increase in the number of
negative sites on the CaC0,1 surface owing to the sorption of the bi-valent
sulfate ions. Such increase could not be obtained on Ca3 (P0 4 ) 2 since this mineral
is apparently saturated with negative sites even in the absence of sulfonate.
This postulate is supported by the observation that introduction of Mg++ into
the solution reduced the adsorption of the cationic surfactant on both CaCO"
and Ca 3 (P0, )2. ·

Lateral Interaction Between Surfactants

An examination of the data given in Figure 1 for the dependence on pH
of electrophoretic mobility of alumina in sulfonate solutions suggests that there .
must be another force responsible for this adsorption in addition to ' electrostatic
attraction below about pH = 7. Adsorption isotherms as well as settling data
obtained for the alumin a/sulfonate systems also suggest such a possibility
(See Figure 4). Both the above properties are found to undergo a sharp increase
>-
I-
U5 -3
z ~

w 'Ul
I-
~ -2
~
1610 100~
"'
6
''20 OF A
w .,,1
·s
"d -~~N_:i:_~:.~~- (!)
z
00

0
I

'O <( ......

:x::
g (.)
0 ~
w
2i"
[%1 11 >
E-<
......
...:i
P'.1 16 10.0~ +I
......
~ _J P'.1
0 w 0
Ul ALUMINA a:: ~
i:l
<t;
o ADSORPTION
DENSITY
x
w
+2 0
H

E-< 6 SETTLING
0 E-<
z INDEX ~ [%1
16'2 +3 ~
0 a MOBILITY 1.0 z (!)
0
0 ::i::
~
_J
I- 0.. .
~ I = 2x10-3 mol d m-3 I- +4 0
pH : 7.2 w P::
(/) E-<
0
+5 [%1
-l3 ~
10 5 4 3
0.1 [%1
10 10 10
EQUILIBRIUM CONCENTRATION/ mol dm-3
Fi gure 4. Adsorption density of d ode c ylsulfonate , ele ctr o p horetic mobility, an d settling r a ';"
of alumina - s odium dodec y lsulfona t e syst e m a s a f unction of t he conce ntra tion of s odium dode -
c y ls ulfo n a t e (Somasundara n , 1964).
72 P . SOMASUNDARAN

at a given adsorption density. This was attributed to lateral association of the

surfactant species in the interfacial region above a critical adsorption density.
Such association to form two-dimensional aggregates called hemi-micelles is
analogous to micelle formation and results from the 'favorable energetics of
removal of the alkyl chains partially from the aqueous environment. The
energy gained due to the process of hemi-micellization has been estimated
in a number of ways. For example, the data given in Figure 5 for the zeta

-100

-so
-60
•
-40
>
E -20
...J
<l 0
;: • C1e
z 20
w
,... A C1s
0 40 0 c,.
Cl.
o C1z
,...
<l 60 A C10
w • NH 4 Ac
N
80

10-1 10-• 10·• 10-• 10-•

CONCENTRATION OF ELECTROLYTE I (mo! dm-3)

Figure 5. Effect of h y drocarbon chain length on the c;-potential of quartz in solution of alkyl-
ammonium acetate and in solutions of ammonium acetate (Somasundaran et al. , 1964).

potential of quartz as a function of the concentration of amines of different

chain lengths can be treated in the following manner with the help of
equation (2) to obtain free energy of hemi-micellization (Lin and Somasunda-
ran, 1971). We rewrite equation (2) with AGads divided into the two terms, one
corresponding to that of electrostatic forces and the other corresponding to
that of the hemi-micellization.

(3)

Concentrations corresponding to hemi-micelle formation (cHMc) were obtained

from the data given in Figure 5 by graphically locating the concentrations at.
which the extrapolations of the straight line portions of the streaming potential
curves intersected the curve for ammonium acetate. Substitution of cHMc for
cb and n cp1icsl> for AG1im, where n is the number of CH 2 and CH 3 groups in the
chain and tph(s l) the average free energy of transfer of 1 mol of CH 2 groups
from the aqueous environment into the hemi-micelles, yields

(4)
RT
 PHYSICO-CHEMICAL ASPECTS OF ADSORPTION
73
The arrangement of equation 4 yields

lg HMC = n~h(sl)
RT
+ /1G + log ~
clec '!:
(5)

A least square plot of log HMC as a function of number of carbon atoms in

the alkyl chain is given in Figure 6. !ph(s l) obtained from this line is - 0.95 kT
comparable to that obtained for free energy of micellization (see Figure 7).
Heat and entropy of adsorption calculated for alkyl chains adsorbed on mineral
particles (Somasundaran and Fuerstenau, 1972) show marked changes at given
concentrations that are in agreement with the postulate of interaction of
surfactant ions to form two dimensional aggregates.

w-3 .------...--.---.----.-...---.-.--.---,..--.----,.----,

~ -4
E 10
"0
E
z
2 cf>h (sl)
1--
<{ -0. 4 12 = 2.303kT
a::
1--
z -5
UJ 10
u
z
0
u
UJ
..J
..J
UJ
u
::E
-6
..'.. 10
~},
:x:

-7
10
8 10 12 14 16 18 20
NUMBER OF CARBON ATOMS
IN THE ALKYL CHAIN, n
Fig u re 6. Least-square plot of log HMC of alkyl-ammonium acetates from streaming potential
data a s a function of the number of . carbon atoms in the chain (Lin and Sornasundaran, 1971) .

Most interestingly, the association was found to produce a net increase

i.n the entropy of the system suggesting a decrease upon aggregation in the
ordering the water molecules- that were originally around isolated surfactant
chains (See Figure 8). Because of the necessity to initiate the surfactant ad-
sorption on solid by some primary adsorption force such as electrostatic
attraction and of the requirement to pack the molecules in an orderly manner,
the extent of aggregation and the concentration at which the aggregation
 P . SOMASUNDARAN
74

AQUEOUS SOLUTION

cfim
</>h(sl}

I ci>t'l.sg)
cfim'
cfitg
<Po
MICELLE (IONIC)

HEMl-MICELLE AT S-L

MICELLE (NON- IONIC)

ADSORPTION AT L-G i/;1. I/II ///,
HEMl-MICELLE AT S-G

HYDROCARBON SURROUNrnNGS

Figure 7. Schematic diagram for free energy of transfer of -CH,- groups from aqueous
solution to various environments (Lin and Somasundaran, 1971).

-20

-19

-18

-17

'0 L'>Sx, HM
-16
E
"'\..:
0u . - 15
::::::
::_ -14
x
OU)

<l
-13

-12

-1 1

-10

-9

-8'--~~~~~~~~~~~~~~~~-,--~~~~~

10- 13 10- 12 10- 11 10· 10 10-•

SULFONATE AOSORPTION DENSITY II mol cm-2)

Figure 8. Partial molar entropy of adsorption of sulfonate as a function of its adsorption

density (Sornasundaran and Fuerstenau, 1972).
 PHYSICO-CHEMICAL ASPECTS OF ADSORPTION 75

becomes significant are dependent, among other things, on such system pro-
perties as pH, temperature, ionic strength, and the chemical structure of the
surfactant.

Chemical Forces
Mainly on the basis of infra-red results obtained for adsorbed surfactant
layers on certain minerals, it has been proposed, for example, that fatty acids
and sulfonates can also adsorb due to covalent bonding (French, et al., 1954,
Peck and Wadsworth, 1965). Also the observation that maximum flotation of
certain minerals with fatty acids is obtained at the point of zero charge (where
the electrostatic attraction should be minimum) has led to dependence on
mechanisms based on covalent bonding between the surfactant species and
the mineral surface species.
Both of the above observations cannot however be considered to provide
sufficient evidence for chemisorption. Identification of a bonding type in an
IR spectrum does not necessarily suggest existence of such bonding on minerals
in surfactant solution because of the possible alterations in chemical state of
the adsorbed surfactant during the preparation of the sample for the spectro-
scopic examination. Dependence of flotation maximum on pH, on the other
hand, can be attributed for a number of systems such as that of hematite/oleate
to the change in chemical state of the oleate species in solution with pH. This
is further described in the next section. Chemisorption has been proposed
to take place also by means of ion exchange. Thus in the case of adsorption of
oleate on fluorite, the surfactant ions are found to release an equivalent amount
of fluoride ions to form a surface layer of calcium oleate (Bahr, et al., 1968;
Bilsing, 1969). Hanna (1975, 1976) also observed salt formation to be the me-
chanism of adsorption for the first layer of Aerosol OT, dodecylbenzenesulfon-
ate and dodecylsulfonate on CaC0 3 and Ca 3 (P0 4 ) 2 • A second layer with the
ionic heads exposed to the bulk solution was considered to be formed in these
cases owing to interchain cohesion. Such a mechanism is supported by the
observation that the contact angle and flotation response obtained were
maximum at concentrations corresponding to the completion of the first layer.

Chemical State of the Surfactant

In addition to micellization and precipitation, hydrolyzable surfactants such
as fatty acids and amines can undergo various associative interactions in
aqueous solutions giving rise to dimers, acid-soaps, trimers etc. (Mukerjee,
1967). The role of these species in determining adsorption has largely been
ignored in the past. Depending upon solution properties such as pH, ionic
strength, temperature, etc., some of these species can be present in significant
amounts to play a governing role in adsorption. Due to the · possibility oi
marked differences in surface activities of these species, one can obtain con-
siderable variation in adsorption with changes, for example, in solution pH.
The major chemical equilibria in a system consisting of an anionic sur-
factant (R-Na+) are
~RH (6)

RH (aq) ~ RH(l) K -1 (7)

sp
76 P. SOMASUNDARAN

RH+ R- ~ R 2H - KAD (8)

2 R- ~ R 2-- Ko (9)

Na+ + R2H- ~ NaHR2 K (10)

Among the various species listed above, the acid-soap complex may be
more surface active than other forms of the surfactant complexes because of
its higher effective molecular size and lower solubility. These species formed
between various ionic and molecular forms of the surfactant are termed
ionomolecular complexes or IM complexes (Somasundaran, 1976).
Associate interactions to form IM complexes have been considered to be
the reason for the deviations in behavior of surfactant solutions in terms of
their conductivity, transport number, partial molar volume, osmosis etc. It is
reasonable to expect such interactions to affect adsorption at different inter-
faces also. As an example, a most widely used hydrolyzable surfactant, namely
oleic acid is considered in detail here. Various equilibria in oleate system to
b e considered here are (Somasundaran et al. , 1977, Jung, 1976):

01- + H + ~ HOl pK" 4.95 (11)

H01 (aq) ~ HOl (1) pKsp 7.6 (12)

HOl + 01- ~ HOl2- pKAD -4.7 (13)

2 01- ~Oh-- pKD -4.0 (14)

HOh- + Na+ "+. NaHOl2 pK -9.35 (15)

The equilibrium diagram showing the activities of various species at 3 X 10-5

mol/dm3 oleate is shown in Figure 9. The precipitation of oleic acid takes place

Figure 9. Equilibrium diagram show ing the activities of various species of oleate at a con-
centration of 3 X 10-s mo! dm-• (Somasundaran et al. , 1977) .
 PHYSICO-CHEMICAL ASPECTS O F ADSORPTION 77

o (KN03): 0
• [KN03 ) =0.2 mol dm·3

40 lc=25 oc

.. 30
~

..ii
~

20

Figure 10. Equilibrium surface pressure o! 3 X 10-• mol dm • potassium o!eate solution in water
and 2 X 10- 1 molar KNOs (Kulkarni and somasundaran, 1975).

.
I
I
3200

7
HEMATITE
[l<-OLEATE)•3x 10- 5 m o l dm-~ ·II 2880 E

0
lKN031•8• 10"' mol dm" 3
f E
80 2560-
~
2240 x
w
...J
0.
I :ii
60 I 1920 0
u
I
I "-
<(
I 0
(/)
I 1600
6
f 0<(
I .._
I 1280 0
I z
0
f ;::
I 960 a:
.<(

·I I ....z
I
I I u
w
I \ 640 0z
I \ u
I \

/
I
I \
,, 320

_,./ ' ..........

4 5 6 8 9 10
pH

Figure 11. Hematite flotation and acid-soap concentration as a function of pH for 3 X 10... mo!
dm·3 oleate solution at an Ionic strength of 8 X 10-• mol dm·• KNO:i (Somasundaran et al., 1977.
78 P. SOMASUNDARAN

at pH = 7.78. Maximum acid-soap complex formation also takes place at this

pH. Even though the numerical value of the concentration of acid-soap species
may be low, it is appreciable enough to affect adsorption processes at the
interfaces (Fuerstenau, et al., 1964). Recent studies on the surface tension of
oleic acid solutions did in fact suggest the presence of highly surface active
species around the neutral pH (Kulkarni and Somasundaran, 1975). As seen
in Figure 10 surface pressure is found to exhibit a maximum at this pH. It is
of interest to note that the surface tension decay rate (dy/dt) also exhibited a
peak around the same pH. It should be pointed out at this. stage that a number
of minerals have exhibited maximum hydrophobicity as measured by the
flotation technique around this pH range when oleic acid is used as collector
(see Figure 11). Correlation of flotation with the species distribution diagram
suggests that the role of acid-soap dimer, soap dimer and precipitated oleic
acid can be significant -in controlling adsorption behavior. In addition, the
formation of various ferric oleate complexes also has to be certainly taken
into account in developing a proper understanding of adsorption phenomenon
in these complex systems.
In the case of amine/quartz system, pH of maximum flotation is above
about 10 (Somasundaran, 1976). Again the amine solutions are found to ' exhibit
maximum surface pressure around this pH. Upon calculation of the distribution
of various species, the above pH is also found to coincide with the pH of
maximum in ionomolecular complex concentrations and the pH of precipitation
of amine.

Miscellaneous Forces
Other factors that can play major roles in certain systems include hydro-
gen bonding, solvation or desolvation of species, and hydrophobic bonding.
Hydrogen bonding can be strong particularly for the adsorption of surfactants
containing phenolic groups (Parks, 1975) and possibly of those containing
hydroxyl, carboxylic and amine groups. Hydrophobic bonding can be important
for adsorption on solids that possess a fully or partially h y drophobic surface.
In this case surfactant molecules can adsorb flat on the hydrophobic sites on
the solid. Such adsorption can also take place on other types of solids that
are originally hydrophilic but have acquired some hydrophobicity owing to
reactions with organic species in solution. Energy involved in this case is
additive and, like in the case of hemi-micellization, adsorption due to it will
increase with the size of the surfactant.
The presence of polymers in solutions has been known to affect adsorption
of surfactants on minerals. In some cases, the adsorption is enhanced, but in
some other cases it is found to be depressed (Somasundaran, 1969; Hanna and
Somasundaran, 1977b).

ADSORPTION IN MICELLAR SOLUTIONS

Adsorption isotherms in micellar solutions are found to often exhibit

special features such as maximum and minimum around critical micelle con-
centration. The presence of a minimum is of much interest for tertiary oil
recovery using surfactant flooding since operation under conditions correspond-
ing to the minimum would lead to minimum surfactant loss during flooding.
 PHYSICO-CHEMICAL ASPECTS OF ADSORPTION 79

Our recent studies on Berea sandstone/Mahogany sulfonate, limestone/Ma-

hogany sulfonate and kaolinite/dodecylbenzenesulfonate have shown presence
of adsorption maximum under certain conditions of salinity (Hanna and Soma-
sundaran, 1977a). The nature of the adsorption isotherm obtained is also
dependent to a great extent on the type of sulfonate used.

o.s r--------.-- - - - - . - - - - - ----,r-------,

I (NaCl)• 10-2 mol dm-3

pH = 4.5± 0.1

<;'E S/L = l :1
tc • (30 ± 0.2)'C
E' 06 ADS. TIME • 24

w
2:
,_
u
<(

: 0.4
l-
o;
~
a
z
a
;:::
Cl.
:5 0.2
"'a
'"
0
0 w . m ~ ~
EOUILISRIUM CONCENTRATION OF MAHOGANY SULFONATE (ACTIVE)/( g dm-3 )

Figure 12. Adsorption isotherms of Mahogany sulfonate- AA (a petroleum sulfonate) on lcaolinite

(Hanna and Somasundaran, 1977).

While adsorption maxima were obtained for Mahogany sulfonate-AA (a

petroleum sulfonate) on previously unwetted kaolinite, isotherms of dodecyl-
sulfonate exhibited only positive slopes but concentrations studied in this
case were restricted to premicellar range due to solubility problems (see
Figures 12 and 13). Increase in ionic strength due to the addition of NaCl

2.5

2
-o-- l0- mol dm-3 KN03 0
_2.0 -o- DIST. WATER
<;'E

~
~1.5
,..
I-
in
z
w
a
z 1.0
a
;:::
Cl.
a:
g
a pH = 4.6 ± 0.1
<X 0.5 S/L • ]o2Q
le= 30 ± 0.2
ADS. TIME • 24 h

0
0 2.0 4.0 6.0 8.0 . 10.0
3
EOUILIBRlUM CONCENTRATION I (m mol dm- )

Figure 13. Adsorption isotherms of dodecylsulfonate on kaolinite (Hanna and Somasundaran, 1977).
80 P. SOMASUNDARAN

pH conditions, possibly due to the non-wetting of pores and the effect of the
presence of pores on interfacial volume from which micelles that are charged
similarly to the solid are excluded (see Figure 14). Agricultural limestone also
increased the adsorption in all cases. Adsorption maximum was sensitive to
the amount of NaCl added. At lower NaCl concentrations, the maximum
existed for Mahogany sulfonate/Berea sandstone system; at intermediate con-
centrations the isotherm exhibited a maximum followed by a shallow minimum;
at still high concentrations the adsorption maximum was not present.
Mineralogical and morphological characteristics of the adsorbent were
found to produce significant effect on adsorption. The porous type of limestone
(Agricultural limestone) possessed a lower adsorption density under natural

1.6 . -- -. - - -- -- - - - - -
•MA HOGANY SULFONATE -AA
t. BEDFORD LIMES TO~JE

o AGRICULTURAL LIMESTO,'IE

-'E
N
1.2

O> 6
E

·-
>-
t:
U)
z 0.8
w
0
z
0
i=
0..
er: 2
0 I I NaCl) = 10- mol dm-3
en
0
<( 0.4 pH = 8.2 ±0.08
SOLIDS CO~IC . = 50%
T01lPERATURE = (30 ± 0.2) °C
ADS. TIME = 4 h

0 ~--~--~--~---~--~----'
0 10 20 30
EQUILIBRIUM CONCrnTRATION I ( g dm-3)

·Figure 14. Adsorption of Mahogany sulfonate-AA on Agricultural limestone and Bedford lime-
stone (Hanna and Somasundaran, 1976) .

pH conditions, possibly due to the non-wetting of pores and the effect of the
presence of pores on interfacial volume from which micelles that are charged
similarly to the solid are excluded (see Figure 14). Agricultural limestone also
exhibited an unexpected adsorption dependence on pH. (see Figure 15). This
was attributed to the silicates that were found to be present in the sample.
Silicates that are concentrated on the surface of the particles following dis-
solution of exposed calcite or magnesite can be expected to be activated by
calcium or magnesium species above neutral pH and thereby cause increased
adsorption of sulfonate on the mineral as the pH is increased. Bedford lime-
stone which does not contain such silicate exhibits decreased adsorption of
sulfonate with increase in pH owing to concurrent decrease in the positive
potential of the mineral particles.
Adsorption studies using clay yielded some interesting new information
that proved helpful in understanding the mechanisms involved (Hanna and
 PHYSICO-CHEMICAL ASPECTS OF ADSORPTION 81
LO~ ------~-----~------.---.

"' BEDFORD LIMESTONE

0 AGRICULTURAL LIMESTONE

0 .8
!(NaCl)= 10-zmol dm-3
TEMPERATURE = (30 ±0.5) °C
SOLIDS CONC. = 50 %
ADS. TIME = 4 h
..s"' 0.6
~
SULFONATE = 12.6 g/dm-3 INITIAL
>- CONCENTRATION
'::: (ACTIVE)
Ul
z
w
0
z
0
~ 0.4
a:
0
U)
0
<t
0

0
0.2

0 ~-----~-----~------~~
8 9 10 II
EQUILIBRIUM pH

Fig ure 15. Data for adsorption of Mahogany sulf onate-AA on A gricultural limestone and Bedf ord
limestone a s a func tion of pH (Hanna and Somasundaran, 1976).

Somasundaran, 1977b). Both equilibration of dry kaolinite with water and

adsorption of sulfonate on it were found to involve a fas t and a slow step, the
latter possibly due to slow dissolution of aluminum species from kaolinite
during prolonged contact of it with water and consequent activation of sulfonate
adsorption. Past studies using kaolinite appear not to have considered the
possibility of an intermediate metastable condition. The effect of increase in
salinity was in general to increase the adsorption of sulfonate mainly due to
the less energetically favorable environment for the surfactant chains in a
saline solution. The effect of the inorganic electrolytes' addition was most
interesting in that the shape of the isotherm was dependent on both the cation
and anion used (see Figure 16). The adsorption capacity was found to increase
in the order NaCl<NH4 COOCH 3 < NH, Cl<NH, N0 3 < KCl in agreement with
the order of increasing cationic size and hydration capacity of cations. Most
importantly, it was observed that an adsorption maximum is obtained in inor-
ganic electrolyte solutions made up of »structure-making« ions. No such maxi-
mum is obtained when there is a predominance of »structure-breaking« inos.
The existence of maximum is attributed to the exclusion of surfactant
aggregates from the structured interfacial region around the particles owing
essentially to their incompatibility with this region. Structure-breaking ions
facilitate transport and accomodation of the surfactant aggregates eliminating
the possibility for such exclusion.
 P. SOMASUNDARAN
82

1: 1 ELECTROLYTES I
7
PURE DODECYLBENZENESULFONATE I No-KAOLINITE
1
pH = 6 .5 ± 0.2 I = 10- mol dm- 3
.:;-6
'E t •
--<r-- KC/
0 t t
E 5
---0-- NH 4 N0 3
t • 100
~ ---0--- NH 4 CI
-. t • w
>- ---0--- NH4 00CCH 3
""
I-
Vi 4
z ----6-- Nac1 0::
w
w
0 Structure >
0
z Breaking Ion 0
Q 3 0::
I- Structure w
0.. Making Ion >-
50
0::
0
(j)
"
_J
0
z
0
0
" ::.
~

0 0~--~--2~0--~-~-4~0--~---6~0--~o

EQUILIBRIUM CONCENTRATION /(m mol din- 3 )

Figure 16. Effect of certain 1 : 1 e lectrolytes (10-1 mol dm-•) on the adsorption of dodecylben-
zenesulfonate on kaolinite at pH = 6.5 (Hanna and Somasundaran , 1977) .

The adsorption isotherms of dodecylammonium chloride on kaolinites were

of simple Langmuir type without a maximum (see Figure 17). Absence of a
maximum can be attributed to lack of micellar exclusion owing to both the
favorable electrostatic attractive forces between the surfactant species (Mu-
kerjee and Anavil, 1975) and the mineral and the structure breaking properties
of the ammonium head groups.

DODECYLAMMONIUMCHLORIDE/ KAOLINITE
DODECYLAMMONIUMCHLORIDE I Na-KAOLINITE

r"
7.0

.'"""" ~"""' '"'"~""

60 e - - - -6 - - - - - - - - - - - - + 1 0 0

.i '"
~ 40 6 Na-KAOLINITE (TREATED)
.,
.,""'
~
0:
. >
~ !(NaCl)= 10- 2 moldm-3 0
50 u
~ 3.0
zo,,, /" pH = 4.7±0.3 .,
0:
~ SOLIDS = 10°/o
0
~
~ z.O 6 _J
TEMP. = (30± 1.0)'C 0
~ ADS TIME = 24h
z
0
:;,
1.0

O.O'-----'----'---'-----'----'---'----'---::':--~o
0 20 . 40 60 80
EQUILIBRIUM CONCENTRATION/( mmal dm-3)

Figure 17. Adsorption isotherms of dodecy lammonium chloride on prewetted kaolinites (untre-
ated and NaCl treated) under natural pH conditions (Hanna and Somasundaran, 1977).
 PHYSICO-CHEMICAL ASPECTS OF ADSORPTION
83
THE ADSORPTION KINETICS

The nature of adsorption kinetics and reversability are dependent to a

large extent on the mechanisms involved. In Figure 18, adsorption density of
sodium dodecylsulfonate is given as a function of time (Somasundaran, 1964).
Adsorption takes place relatively fast as expected for a case of physical ad-
sorption. Oleate adsorption on hematite is also found to occur rapidly at pH = 8
(Kulkarni and Somasundaran, 1976) (Figure 19). However, the same system
is found to exhibit a markedly different type of kinetics at a pH of 4.8 (Figure

~ soL~)>----0-----'----
' --'-'-~'--'--'--'-1-q
CD;:-
0:: 'rn
0 40
I/)"'
0 "-
<{ :::30
w <(
.... z
<( :E20
z :::i
0 --'
~ <( 10
:::i z
Vl 0 0 ~)_..._~_~_...___._~--'---'--'---'----'
0 2 4 6 B 10 12 14 16 IB 20 22
TIME/h
Figure 18. Adsorption of sodium dodecylsulfonate on alumina as a function of time (Somasun-
daran, 1964).

pH 8 .0
3- 1
fKNO:J=2x16 mot dm- 3
5
[K-OLEATE]=1.5x10 mol dm·l

• • 75 "C •
•

I I I I
L
0 5 10 15 20 25
AGITATION TIME I min
Figure 19. Adsorption of oleate on hematite as a function of time at pH ~ 8 (Kulkarni and
Somasundaran, 1975) .
 P. SOMASUNDARAN
84

0
E
::!..
:::::: 2
>-
1-
en
z
w
0
z
Q
l-
a..
0:::
0 pH=4.8
en
0
<! [KNOiJ = 0
-5 3
[K- OLEATE]=l.5x 10 mol dm-

100 150 200 250

AGITATION TIME I min
Figure 20. Adsorption of oleate on hematite as a function of time at pH = 4.0 (Kulkarni and
Somasundaran. 1975).

20). Equilibrium is not attained in this case even for several hours. Evidently
adsorption of oleic acid on hematite involves mechanisms that are different
than that of oleate or acid soap. Implication of this observation in regard to
the daagcr of the common practice of selecting equilibration time for adsorption
experiments from tests conducted under only one se'.; of conditions is to be noted.
Acknowledgement. - The author wishes to acknowledge the National Science
Foundation (ENG-76-08756), Amoco Production Company, Gulf Research & Develop-
ment Company, Marathon Oil Company, Mobil Research & Development Company,
Shell Development Company, Texaco, Inc., and Union Oil Company of California for
support of this work.
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 PHYSICO-CHEMICAL ASPECTS OF ADSORPTION
85
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d a ran and R. B. Grieves (Eds.) Advances in Interfacial Phenomena, AIChE
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86 P. SOMASUNDARAN

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SAZETAK
Fizicko-kemijski aspekti adsoprcije povrsinski aktivnih tvari na mineralima
P . Somasundaran
Diskutirani su osnovni principi i neki posebni aspekti adsorpcije na mineralima.
Detaljnije su razradene uloge elektrostatskih sila, lateralnih interakcij a izmedu
surfaktanata, kemijskih i ostalih sila kao i uloga kemijskog stanja surfaktanata.
Istaknuta je vaznost prethodne obradbe mineralnih sistema koja utjece na njihovo
elektrokineticko ponafanje kao i prisutnost ostalih nabijenih cestica u otopini aka
elektrostatske sile imaju znatniju ulogu. Nagli porast u elektroforetskoj pokretlji-
vosti za odredenu gustocu adsorpcije i stanovite uvjete obja5njava se stvaranjem
micela, a pojava maksimalne flotacije nekih minerala, sa surfaktantima podloznim
hidrolizi, u podrucju nultog naboja pripisuje se stvaranju kovalentnih veza u z moguce
stvaranje polimera. Ostali faktori kao sto su vodikova veza, solvatacija, desolvatacija
specija i hidrofobno vezanje takoder su spomenuti. Posebna pafoja posvecena je
adsorpciji u micelarnim otopinama i adsorpcijskoj kinetici.
HENRY KRUMB SCHOOL OF MINES,
COLUMBIA UNIVERSITY, Pris pjelo 18. prosinca 1978.
NEW YORK, NEW YORK 10072, USA