FIG. 3. Adsorption isotherms of the conventional surfactants and the gemini surfactants on montmorillonite at 25◦ C in 0.01 M KBr. (a) C10 TMAB and
C10 gemini; (b) C12 TMAB and C12 gemini; (c) C14 TMAB and C14 gemini; (d) C16 TMAB and C16 gemini.
268 LI AND ROSEN
TABLE 1
Maximum Surfactant Adsorption onto Montmorillonite at 25◦ C from 0.01 M KBr and the Stability of the Resulting Dispersion
CMCa Amin
a Cs (max) Ceq (max)c Initial absorbance t1/2
Surfactant (mol/dm3 ) (A2 ) (mol/g Clay) (mol/dm3 ) (A0 ) (min) Abs/A0
C10 TMAB 6.22 × 10−2 70.6 7.43 × 10−4 1.82 × 10−2 0.17 9.96 /
C10 gemini 7.95 × 10−4 101.6 7.20 × 10−4 6.59 × 10−3 0.73 22.1 0.41
C12 TMAB 9.29 × 10−3 67.6 8.13 × 10−4 3.61 × 10−3 0.47 11.4 /
C12 gemini 1.64 × 10−4 89.8 7.54 × 10−4 1.43 × 10−3 1.56 >60 0.61
C14 TMAB 2.47 × 10−3 63.4 8.27 × 10−4 6.47 × 10−4 0.60 12.6 /
C14 gemini 7.82 × 10−6 21.7 8.12 × 10−4 1.90 × 10−4 1.84 >60 0.69
C16 TMAB 8.20 × 10−4 59.3 8.92 × 10−4 1.64 × 10−4 0.75 13.0 /
C16 geminib 2.25 × 10−6 9.3 / / / / /
a Literature values at 30◦ C in 1.25 × 10−2 M KBr [Trap, H. J. L., and Hermans, J. J., Koninki Ned Akad Weten. Proc. Ser B 58, 97 (1955)]: C TMAB, 5.9 × 10−2 ;
10
C12 TMAB, 1.08 × 10−2 ; C14 TMAB, 2.1 × 10−3 .
b Maximum amount adsorbed on clay cannot be reached due to poor solubility of surfactant in water.
c C (max) is the equilibrium surfactant concentration in solution phase at maximum amount adsorbed.
eq
change in C) is taken as 1 for the gemini surfactants because as the number of carbons in the alkyl chain increases. Table 1
the surfactant concentrations used to calculate Amin are much shows that the Amin values decrease with increase in the length
less than one-tenth of the ionic strength (i.e., 0.01 M). For the of the alkyl chain for the gemini surfactants, the same as for
conventional surfactants, n is taken as 1 when the surfactant the conventional surfactants studied here and for other conven-
concentrations used to calculate Amin are less than one-tenth of tional surfactants (16b). The very large slopes (and the very
0.01 M, otherwise, the value of n can be obtained by use of the small Amin values) for the C14 and C16 gemini surfactants have
following equation (17): been observed before and may be due to multilayer formation
Csurf of the surfactants at the air/solution interface (18).
n=1+ , [4] Adsorption isotherms of the conventional surfactants and
Csurf + I S the geminis onto montmorillonite at 25◦ C from aqueous 0.01
where IS is the ionic strength of the added electrolyte. Csurf is M KBr solution are shown in Fig. 3a–d. Data are listed in
the average surfactant concentration used for [∂γ /(∂ log C)]T . Table 1.
The slopes of the plots in Fig. 1 indicate that the concentra-
tion of surfactant at the air/aqueous solution interface increases
FIG. 6. Adsorption of 2-naphthol and 4-chlorophenol onto surfactant-treated clay at 25◦ C in 0.01 M KBr. (a) C10 TMAB and C10 gemini; (b) C12 TMAB and
C12 gemini; (c) C14 TMAB and C14 gemini; (d) C16 TMAB and C16 gemini.
The typical S-shaped isotherm (16c) is apparent only in are shown on Table 1. Noteworthy is the much lower concen-
the case of C10 TMAB. For the other surfactants, the amount tration of gemini, about 13 that of the conventional surfactant
adsorbed on the clay increases sharply to a maximum with with the same alkyl chain length, needed to achieve this max-
increase in equilibrium surfactant concentration. For both the imum adsorption. This indicates that the gemini surfactant is
gemini and the conventional surfactants, the maximum amount much more efficient than the conventional surfactant at achiev-
of surfactant at the clay/aqueous solution interface, Cs (max), ing this maximum adsorption on the montmorillonite. The data
increases with the length of hydrophobic chain. The maxi- also show that, in spite of the fact that the gemini have two
mum amount of surfactant absorbed onto the clay is larger quaternary nitrogen groups that can adsorb onto negative sites
than the CEC of the clay in the case of C12 TAMB, C12 gemini, onto the montmorillonite, the molar adsorptions of the gemini
C14 TMAB, C14 gemini, and C16 TMAB. This indicates that al- and conventional surfactants are almost identical. This indicates
though cation exchange plays a major key role in the adsorption, that only one of the hydrophilic groups in the gemini molecule is
hydrophobic bonding between chains also occurs and becomes adsorbed onto the clay and that the second hydrophilic group is
stronger as the hydrophobic chains become longer. The data on presumably oriented towards the aqueous phase. This mode of
the surfactant concentration in the solution phase Ceq (max) at adsorption would be in marked contact to the adsorption of the
which this maximum adsorption of surfactant, Cs (max), occurs conventional surfactants, which would also have their quaternary
270 LI AND ROSEN
nitrogens oriented toward the clay, but with their hydrophobic TABLE 2
groups oriented towards the aqueous phase. Pollutant Adsorption onto Surfactant-Treated Montmorillonite
The adsorption of the gemini surfactants onto the montmo-
Max. amount Pollutant/
rillonite would consequently make the surface of the latter hy- of pollutant surfactant
drophilic, while the adsorption of the conventional surfactants adsorbed ratio
would make the surface of the latter hydrophobic. That this is Pollutant Surfactant Cs (mol/g) (mol/g) (mol/mol)
indeed the case is shown by the absorbance in the visible region
of aqueous suspensions of the clay with the maximum amount 2-Naphthol C10 TMAB 7.43 × 10−4 1.48 × 10−4 0.20
C10 gemini 7.20 × 10−4 2.61 × 10−4 0.36
of surfactant adsorbed onto it (Fig. 4). After the clay suspension C12 TMAB 8.13 × 10−4 1.73 × 10−4 0.20
was shaken for 24 hrs, its absorbance was immediately mea- C12 gemini 7.54 × 10−4 2.95 × 10−4 0.38
sured in the visible at 580 nm. From the absorbance data, the C14 TMAB 8.27 × 10−4 2.09 × 10−4 0.25
clay suspension with the adsorbed gemini surfactant is much C14 gemini 8.12 × 10−4 3.14 × 10−4 0.38
more stable than that with the adsorbed conventional surfactant. C16 TMAB 8.92 × 10−4 2.40 × 10−4 0.27
C16 geminia / / /
In the case of the clay with adsorbed conventional surfactant, the
p-Chlorophenol C10 TMAB 7.43 × 10−4 4.33 × 10−5 0.058
absorbance rapidly decreases with time, indicating rapid floccu-
C10 gemini 7.20 × 10−4 1.68 × 10−4 0.24
lation of the clay as a result of its hydrophobic surface. In the C12 TMAB 8.13 × 10−4 7.01 × 10−5 0.084
case of the clay with adsorbed gemini surfactant, the solution C12 gemini 7.54 × 10−4 2.08 × 10−4 0.28
remains turbid for an extended period, due to dispersion of the C14 TMAB 8.27 × 10−4 1.10 × 10−4 0.13
clay in the aqueous phase as a result of the positive charge on C14 gemini 8.12 × 10−4 2.42 × 10−4 0.29
C16 TMAB 8.92 × 10−4 1.39 × 10−4 0.16
the surface of the particles and the hydrophilic surface character
C16 geminia / / /
imparted by the second hydrophilic group oriented away from
the clay surface. Figure 5 illustrates the expected gemini adsop- a Maximum amount adsorbed on clay can not be reached due to poor solubility
tion compared with that of conventional surfactant. The initial of surfactant in water.
absorbance, A0 , and t1/2 (the time when the absorbance reduces
to half of its initial value) of the gemini-treated clay suspen-
sion are both larger than those of its corresponding conventional factants with the carbon number of their hydrophobic chain, the
surfactant (Table 1). maximum adsorbed amount and ratio of the amount of pollutant
As a result of the increased adsorption with increase in the adsorbed to the mole of surfactant adsorbed also increase with
length of the hydrophobic group to values above the CEC, the the carbon number of the surfactant’s alkyl chain. The decrease
initial absorbance, t1/2 , and Abs/A0 (where Abs is the absorbance of the adsorption amount of either pollutant with increase in the
value at 60 min) increase from C10 TMAB to C16 TMAB and from equilibrium surfactant above its critical micelle concentration
C10 gemini to C14 gemini (Table 1). after the maximum adsorption amount has been reached is pre-
sumably due to solubilization of the pollutant in the micelles in
Adsorption of 2-Naphthol and 4-Chlorophenol the aqueous phase (12).
onto Montmonrillonite with Adsorbed Layers This increased adsorption of the pollutant onto the gemini,
of Gemini or Conventional Surfactant compared to that of the conventional surfactant, shows that the
Adsorption isotherms of 2-naphthol and 4-chlorophenol onto former is more effective than the latter in removing pollutants
montmorillonite with the maximum amount of the adsorbed from aqueous media. The observation that the maximum ad-
gemini or conventional surfactant on it are shown in Fig. 6a–d, sorption of the gemini surfactant onto the clay occurs at about 13
and the data are listed in Table 2. They show that the amount the concentration of the conventional surfactant in the solution
of 2-naphthol adsorbed per gram of clay at the point where the phase (Table 1) shows that the gemini is also more efficient at
surfactant is adsorbed at its maximum is 1.5 times for the gem- removing the pollutant from aqueous media.
ini surfactant, compared to that adsorbed onto the conventional
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