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Journal of Luminescence 82 (1999) 315}319

Ion exchange between divalent counterions in anionic


micellar solution
Joa o Baptista Sargi Bonilha, Antonio Claudio Tedesco*, Daniela M.A.F. Navarro,
PatrmH cia Maria Nassar
Departamento de Qun& mica da Faculdade de Filosoxa, CieL ncias e Letras de RibeiraJ o Preto, Universidade de SaJ o Paulo,
14040-901, RibeiraJ o Preto, Brazil
Received 7 January 1998; received in revised form 4 May 1999; accepted 4 May 1999

Abstract
The ion exchange between divalent cations in anionic micellar systems were investigated by a #uorescence quenching
technique using the anionic ruthenium complex RuL\ (L"4, 4-dicarboxy-2, 2-bipyridine) as an extramicellar probe

and the N, N-dimethyl-4, 4-bipyridinium ion (MV>) as the quencher. Competitive ion exchange at the micellar surface
between the divalent quencher counterion (MV>) and the divalent hexamethylethylenediammonium (HED>) counterion can be adequately described with a simple pseudophase ion-exchange formalism. The counterion exchange selectivity
coe$cients are K+4&#""1.3 and 1.4 for HED-decyl sulfate [HED(DeS)] and HED-dodecylsulfate [HED(DS)]
micelles, respectively. These results show that the MV> cation only slightly more strongly bound to the micelle
aggregates than the HED> cation.  1999 Elsevier Science B.V. All rights reserved.
Keywords: Ion exchange; Fluorescence; Hexamethylethylenediammonium dodecyl sulfate; N, N-dimethyl-4, 4-bipyridinium
dichloride

1. Introduction
The properties of micelles formed by surfactants
like sodium dodecyl sulfate (SDS) have been
studied for many years and the in#uence of organic
and inorganic additives has been reported [1}3].
The presence of organic and inorganic cations
can a!ect the composition of the micellar surface, due to the competitive ion exchange that
occurs between these ions and the micellar counterions [4].

* Corresponding author. Fax: #55-16-6338151.


E-mail address: atedesco@usp.br (A. Claudio Tedesco)

Several groups have studied the competitive


binding of counterions to micellar interfaces in the
presence of two (or more) counterions [5}12]. All of
these works consider the micelle to be a distinct
phase of the solution and describe the ion exchange
process by an equilibrium of the type:

Z
VW Z
W X #> )8
W X #> .




Z
Z
V
V

(1)

K is the counterion exchange selectivity coe$cVW


ient, de"ned as

   

8W8V [> ]
h
V
 ,
K "
VW
[X ]
h

W

0022-2313/99/$ - see front matter  1999 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 2 3 1 3 ( 9 9 ) 0 0 0 5 0 - 2

(2)

316

J.B.S. Bonilha et al. / Journal of Luminescence 82 (1999) 315}319

where the subscript `fa refers to the analytical concentration of the counterions free in the intermicellar aqueous medium and h and h are the fraction
V
W
of the micellar surface charge compensated by the
bound counterions.
In previous works the selectivity coe$cients
for monovalent}monovalent and monovalent}
divalent counterion exchange were analyzed employing photophysical techniques [13}16].
Counterion exchange coe$cients for sodium
dodecyl sulfate micelles were obtained from
steady-state measurements, using cationic quenchers like Cu>, N, N-dimethyl-4, 4-bipyridinium
(MV>),
and
N-methyl-4-cyanopyridinium
(MCP>). Fluorescence quenching data for the
extramicellar anionic ruthenium complex, RuL\

(L"4, 4-dicarboxy-2, 2-bipyridine) were treated
employing the pseudophase ion-exchange formalism. The values obtained for the selectivity coe$cients point to an in#uence of the hydrophobic
character of the quencher ions present in anionic
micellar solutions. This is the case, for example, for
the selectivity coe$cients determined for
MV>/Na> (K "7.0$1.0) and for Cu>/Na>
V,
(K "1.2$0.1) counterion exchange at the surV,
face of SDS micelles [15].
In the present paper, we describe an extension of
these studies to anionic surfactants (decyl- and
dodecyl- sulfates) that have a divalent hydrophobic
counterion, HED> (N, N, N, N, N, N-hexamethylethylenediammonium), rather than Na>.
We have used RuL\ and MV> as the probe and

quencher, respectively, to investigate the divalent}
divalent MV>/HED> ion-exchange process at
the surface of HED-decylsulfate [HED(DeS) ] and

HED-dodecylsulfate [HED(DS) ] micelles.

2. Experimental section
2.1. Materials
Sodium dodecylsulfate, SDS (Aldrich), was puri"ed by recrystallization from ethanol and purity
checked by surface tensiometric determination of
the critical micelle concentration (cmc). N, NDimethyl-4, 4-bipyridinium dichloride (methyl
viologen, MVCl ) was purchased from Sigma, and


the sodium salt of tris-(4, 4-dicarboxy-2, 2-bipyridine) ruthenium (II), RuL\, was synthesized

as previously described [14]. All solutions were
prepared in ultrapure water from a Millipore
system and all other solvents were analytical
grade.
2.1.1. Preparation of hexamethylethylenediammonium
iodide (HEDI2)
A mixture of 18 ml (120 mmol) of N, N, N, Ntetramethylethylenediamine (BDH) and 15 ml of
methyl iodide dissolved in 70 ml of dry ethanol was
stirred for 16 h at room temperature. Recrystallization of the resultant white solid from ethanol
(active charcoal) provide 42.6 g (80% yield) of hexamethylethylenediammonium iodide. The purity
was veri"ed by C, H, N microanalysis (C H N I .
   
1/2H O; found: C, 23.42; H, 5.64; N, 6.52; cal.: C,

23.37; H, 5.66; N, 6.70%), by iodide ion titration
[17], which provide an apparent molecular weight
of 409 g/mol, and by H NMR (80 MHz, D O):

d 4.10 (s, 4 H), d 3.35 (s, 18 H).
2.1.2. Preparation of hexamethylethylenediamonium
alkyl sulfates [HED(DS)2 and HED(DeS)2]
Decyl and dodecylsulfate salts of HED> were
precipitated by metathesis from the corresponding
solutions of sodium alkyl sulfate and hexamethylethylenediammonium iodide. In each case,
approximately 72 g of sodium alkyl sulfate were
dissolved in 500 ml of 95% ethyl alcohol. Then 50 g
of hexamethylethylenediammonium iodide was
added and the resulting mixture stirred for 2 h at
room temperature. The surfactants were recrystallized twice from ethanol, subjected to Soxhlet extraction with anhydrous acetone for 12 h, washed
with ca. 1 l of chilled distilled water to remove all
traces of iodide ion and dried in vacuum over
P O . The absence of residual iodide ion in the
 
detergent was veri"ed by the lack of precipitation
with aqueous silver nitrate solution and by negative
Lassaigne test [18]. Elemental analyses were satisfactory for both detergents: C H N S O .  H O
      
found: C, 55.72; H, 10.50; N, 4.09; calc. C, 55.99; H,
10.50; N, 4.08%; and C H N S O found: C,
    
54.02; H, 10.35; N, 4.47, calc. C, 54.19; H, 10.32; N,
4.52%.

J.B.S. Bonilha et al. / Journal of Luminescence 82 (1999) 315}319

2.2. Methods
The cmc values for HED(DeS) and HED(DS)


were obtained by surface tension and speci"c conductivity techniques, employing a Thomas model
70535 Du NouK y Surface Tensiometer, equipped
with a Pt ring, and an Analion C-701 conductimeter, respectively. Successive aliquots of a concentrated stock solution of HED(DeS) or

HED(DS) prepared in water with HEDI


(0}0.035 M) were added to a thermostatted cell
containing water or an aqueous solution of HEDI .

Critical micelle concentrations (cmc) were determined from plots of apparent surface tension versus
log [surfactant], or from the speci"c conductance
as a function of the surfactant concentration, at
453C, 533C and 633C.
The #uorescence quenching experiments with
RuL\ as probe were performed in the absence and

in the presence of micelles, using MV> as quencher. The solutions, contained in thermostatted
#uorescence cuvettes, were prepared with
RuL\ (3;10\ M), HEDI (0.0}0.035 M), and


HED(DeS)
or HED(DS)
(0.01}0.035 M).


Aliquots of a concentrated stock solution of the
quencher (0.4 M) were added directly to the sample
cuvette via a calibrated Hamilton microsyringe,
and the emission intensities were registered after
each addition. Fluorescence measurements were
performed at 453C, 533C and 633C on a PerkinElmer LS-5B spectro#uorometer, equipped with
a thermostatted sample holder.

3. Results and discussion


Critical micelle concentrations (cmc) of
HED(DeS) and HED(DS) obtained by surface


tension and speci"c conductivity are listed in
Table 1. In surfactant systems with multivalent ions
the Kraft point is usually increased and the surfactants often precipitate at room temperature. An
increase in the number of the carbon atoms in the
alkyl chain also leads to a reduction in the solubility of these compounds. Consequently, the temperatures used to determine cmc values were: 453C,
533C and 633C for HED(DeS) , and 533C and 633C

for HED(DS) . The cmc values found for these


317

Table 1
Values of cmc and a determined by surface tension and conductivity for HED alkyl sulfate detergents.
Surfactants

[HED>]
mM

(3C)

cmc
(mM)

HED(DeS)


0.0

25
25
25

45
45
53
45
53
63

6.48
7.20
6.60
3.00
3.30
3.40

(c)
(C)
(C)
(C)
(C)
(C)

0.0

53

25
25

53
63

0.28
0.23
0.10
0.11

(c)
(C)
(C)
(C)

HED(DS)


0.11
0.11

0.10
0.10

(c) " measured by surface tension; (C) " conductivity.

surfactants are lower than those of the same surfactants with Na> as counterion. For both surfactants, the dependence of the cmc on temperature is
relatively small. Increasing the chain length, from
decyl to dodecyl, decreases the cmc, as does the
addition of HEDI .

The values of a may be estimated from the ratio
of slopes of the linear regions of plots of speci"c
conductance as a function of surfactant concentration, above and below the critical micelle concentration [19], as well as from Corrin}Harkins plots
[20]. The a values found by these two methods are
similar (Table 1) and lower than that of 0.25 found
for SDS [21], due to the in#uence of the divalent
organic counterion on the properties of the
micelles.
As shown in the previous studies [14], the
quenching of the luminescent probe RuL\ by

MV> obeys the Stern}Volmer relationship in homogeneous solution:
I3/I"1#K [MV>],


(3)

where I3 and I are the #uorescence intensities in


the absence and presence of the quencher, respectively, and K is the Stern}Volmer quenching
14
constant. The quenching reaction is an electrontransfer process from the excited ruthenium
complex to the quencher, forming the viologen
cation radical [22].

318

J.B.S. Bonilha et al. / Journal of Luminescence 82 (1999) 315}319

The variation of the Stern}Volmer quenching


constant with salt concentration follows the extended Debye}HuK ckel relationship [23]:

where h
and h are the fractional coverages
&#"
+4
of the aggregate surface by HED> and MV>
given by

log K "log K3 !16 A (k)/(1#5.8k), (4)


14
14
where k is the ionic strength, A is a constant
(A"0.525 at 453C; 0.531 at 533C and 0.538 at
633C) and K3 is the Stern}Volmer constant at zero
14
ionic strength. The experimental variation of
K with ionic strength in aqueous solution was
14
employed to determine the K3 values: 45 700 M\
14
at 453C, 51 600 M\ at 533C and 65 600 M\ at
633C.
The basic assumption of the method employed
[13}16] is that the tetraanionic probe RuL\ is

completely excluded from the negatively charged
micelle, while the viologen cation partitions between the micellar and aqueous phases. Thus upon
addition of anionic micelles, the concentration of
the quencher in the aqueous phase decreases due to
binding to the micellar surface, attenuating the
quenching e$ciency. Considering that the quenching e$ciency is dependent on the concentration of
free viologen cation in the aqueous phase,
[MV>] , and that the quenching of the lumines
cence of RuL\H by MV> follows normal

Stern}Volmer kinetics, the equation describing the
quenching is then

h "[HED>] /C ,
(8)
&#"
 "
h "[MV>] /C ,
(9)
+4
 "
h3 "h #h "(1!a).
(10)
&#"
&#"
+4
The micellar fractional coverages and the bound
and free micelle counterion concentrations are related by the pseudophase ion exchange mass balance relationships:

I3/I"1#K [MV>] .
(5)
14

The total concentration of added quencher,
[MV>] , is related to the [MV>] and the con

centration of micelle-bound cation, [MV>] , by

the mass-balance relationship:

The K
values obtained from the experi+4&#"
mental data are 1.3 for HED(DeS) (10}35 mM

detergent; 45}633C) and 1.4 for HED(DS)

(5}35 mM detergent; 53}633C). In Fig. 1, representative Stern}Volmer plots for the quenching of
RuL\ by MV> are presented; the curves corres
pond to the predictions of the model (Eqs. (4)}(12))
for MV>/HED> ion exchange in HED(DS)

micelles. Changes in the alkyl chain length have no
signi"cant e!ect on K
, consistent with pre+4&#"
vious "ndings that the ion exchange process at the
micellar interface is not in#uenced by the micelle
size [12].
The fact that the experimental values of
K
are only slightly longer than unity points
+4&#"
to a similar a$nity of the alkylsulfate micelles surface for these two divalent organic cations, despite
the large di!erence in chemical structure and
charge distribution in the MV> and HED> ions.

[MV>] "[MV>] #[MV>] .


(6)



The appropriate value of K in the presence of
14
anionic micelles is calculated from the ionic
strength dependence of K (Eq. (4)), using the
14
K3 values determined in homogeneous solution
14
and the e!ective intermicellar ionic strength (k ,

see below). This value of K is used to calculate
14
[MV>] iteratively from the experimental I3/I

data. The corresponding counterion exchange selectivity coe$cient (K
) is then calculated from
+4&#"
the relationship:
K
"(h [HED>] )/([MV>] h ),
+4&#"
+4

 &#"

(7)

(11)
[HED>] "(1!a)C !h C ,

"
+4 "
[HED>] "aC #cmc#[HEDI ] #h C .

"
 
+4 "
(12)
In these equations, [HEDI ] is the added com 
mon counterion salt and C is the concentration of
"
aggregated HED(DeS) or HED(DS) , given by:


C "C !cmc.
"
2
As discussed previously [6,7,12}16], the e!ective
ionic strength in the aqueous phase is determined
by the ionic concentrations at the midpoint between micelles, which, in the present case, leads to
k "2[HED] #2[MV>] #cmc#[HEDI ] .



 
(13)

J.B.S. Bonilha et al. / Journal of Luminescence 82 (1999) 315}319

Fig. 1. Stern}Volmer plots of the quenching of RuL\ emission



by MV> in HED(DS) micellar solutions in the presence of

HEDI (25 mM) at 633C. Surfactant concentrations: () 5 mM,

() 10 mM, () 25 mM and () 35 mM.

Acknowledgements
This work was supported by grants from the
Fundac7 a o de Amparo a` Pesquisa do Estado de Sa o
Paulo, FAPESP (projects 91/0480-1 and 94/3505-3)
and PADCT-FINEP (Project no. 65-92-0063-00).
D.M.A.F. Navarro and P.M. Nassar acknowledge
fellowship support from FAPESP.
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