16436 J. Phys. Chem.

1995,99, 16436-16441

Intermolecular Interactions between Surfactants Coadsorbed on Electrodes

Wenfeng Peng and James F. Rusling*

Department of Chemistry (U-60), University of Connecticut, Storrs, Connecticut 06269-3060
Received: July 11, 199.5@

Reactions of electroactive species adsorbed on electrodes from surfactant solutions are influenced by coadsorbed
nonelectroactive surfactant. Theory and methods are described to provide Frumkin interaction parameters
between all amphiphilic species adsorbed onto the electrode in such situations, using cyclic and square wave
voltammetry (SWV) and assuming reversible electron transfer. A simple equation to estimate surface
concentrations from reversible SWV curves is presented. The method was applied to the electroactive
amphiphile dimethyl(ferrocenylmethy1)hexadecylammonium ion (Fc-C16) adsorbed onto glassy carbon
electrodes from aqueous solutions containing hexadecyltrimethylamonium bromide (CTAB). Results were
consistent with head-down orientations of these surfactants on a glassy carbon electrode. While mixed adsorbate
layers were formed, a small preference for adsorption of Fc-C16 was found in the presence of CTAB.
Interaction parameters between Fc-C 164%-C 16, Fc-C 16/CTAB, reduced and oxidized forms of Fc-C 16, and
CTAB/CTAB were attractive, suggesting favorable hydrophobic interactions. Interactions of the +2 charged,
oxidized Fc-C 16 with itself and with CTAB were repulsive, suggesting that Coulombic head group repulsion
overcomes hydrophobic interactions between these species.

Introduction
Microheterogeneous fluids containing surfactants have been
suggested as less toxic, less costly substitutes for organic
solvents in synthetic applications.' Surfactant-based fluids such
as micellar solutions and microemulsions can be used to enhance
rates of mediated electrochemical reactions by coadsorption of
nonpolar reactants with surfactant on the e l e ~ t r o d e . ~As
-~ a
basis for predicting dynamics in such systems, molecular
interactions and dynamics of surfactants and coadsorbates on
electrodes need to be understood.
We recently used flow voltammetry to measure adsorption-
desorption dynamics of electroactive amphiphiles on carbon
electrodes5 For the (ferrocenylmethy1)alkyldimethylammonium
ions used, full coverage on the electrode is associated with a
head-down orientation.
The ideal Langmuir isotherm assumes a homogeneous surface
and no intermolecular interaction^.^,' Nearly all surfaces are
microscopically heterogeneous to some extent. Furthermore,
hydrophobic interactions between adsorbed amphiphilic mol-
ecules become significant as fractional coverage of the surface
approaches unity. Indeed, dependence of adsorption free
energies on chain length3s5-*is a manifestation of a hydrophobic
component to the driving force. The Frumkin isotherm consid-
ers intermolecular interactions by including interaction param-
eters. Facci showed that adsorbed ((ferroceny1)methyl)-
dimethyloctadecylammonium ions lie flat on hydrophobic
platinum electrodes coated with iodine, and demonstrated
excellent fits with the Frumkin i ~ o t h e r m . ~
In this paper, we describe intermolecular interactions between
an electroactive amphiphile coadsorbed on an electrode and a
nonelectroactive surfactant. Starting with the Frumkin isotherm,
theory for cyclic and square wave voltammetry was developed
for this task.
Theory
The Frumkin isotherm can be expressed in terms of the
fractional coverage (0) of the surface by an adsorbatelo
'Abstract published in Advance ACS Abstracts, October 1, 1995.
0022-365419512099- 16436$09.0010
*i
pici= -exp(gO,)
1 - ei
where Bi = T,/T,, Ti is the amount of species i adsorbed on the
electrode per unit area at concentration Ci, and rm is the
saturation surface concentration. pi is the adsorption coefficient
related to the Gibbs energy of adsorption AGi by
pi = exp( - AGi/RT) (2)
where R is the gas constant and Tis the temperature in kelvin.
The interaction parameter g in eq 1 expesses the way in which
increased surface coverage changes the adsorption energy. If
g is positive, the interactions between two adsorbed species are
repulsive. If g is negative, the interactions are attractive.
Consider two species, R and S, coadsorbed on an electrode
surface. R is electrochemically active and can be oxidized to
species 0 via a Nemstian n-electron transfer. S is a nonelec-
troactive surfactant. During an electrochemical perturbation
(e.g., cyclic voltammetry) three species will coexist on the
electrode surface, S, R, and 0. The appropriate isotherms are
expressed as follows' ' . I 2
where goo, gRR, goR, gos, and gRS are the interaction parameters
for pairs of molecules denoted by the subscripts.
We assume for the present work that pi, Ti (in the absence
of electrolysis), and gi are independent of electrode potential E
in order to limit the complexity of the problem. These are
reasonable assumptions since the free energy of adsorption of
the ferrocene amphiphile used in this work shows only a weak
dependence on electrode p~tential.~ Dividing eq 3 by eq 4 gives
0 1995 American Chemical Society
Surfactants Coadsorbed on Electrodes J. Phys. Chem., Vol. 99, No. 44, 1995 16437

cdl

j-+;+L
Cf
The concentrations of 0 and R on electrode surface can be
related to electrode potentials by the Nemst equation, Figure 1. Simple equivalent circuit for an irreversibly attached reactant.
R, is the total uncompensated resistance, cdl is the double layer
capacitance, and Cfis the Faradaic pseudocapacitance.
CO = exp[(%)(E - If')]
-
CR

where EO' is the formal potential for the O/R couple.

For strong adsorption where an adsorbed layer of R or 0
forms at solution concentrations so small that the contribution
from diffusion of dissolved R or 0 to the Faradaic current (i) Equations 11 and 13 can be used to show that the full width at
is negligible, then half-height of the cathodic or anodic wave is

(7) AE,,, = - ("'

nF 2 ln- 1 +
-WW+e*dv) (16)

The initial conditions at t = 0 are where Y = [l - {4/(8*6 8))1112. +

Coadsorption of S within a mixed adsorbed layer of 0, R,
and S can have a large influence on the voltammograms since
fractional coverages 80, OR, and 8* decrease when 8s > 0. As
and we have 8s increases, the peak currents decrease and the shapes of the
voltammograms change. As shown by eq 15, the peak potential
ro+ R
r = r* (9) depends on the relative strength of adsorption of the redox
couple, and interaction coefficients and fractional coverage of
We assume that 0 and R have equal maximum surface
concentrations, Tm. Dividing eq 9 by rm of 8*6 (eq 16). When 6 = 0, or 8* 0,-
all three species. The peak width, however, is only a function

80 + 8 R = 8* (10)

where 8* = T*/T,. Let 80/8* = J the fraction of the initial R

on the surface that has been oxidized. From eqs 5, 6, and 10 This peak width is identical to that predicted with the Langmuir
isotherm.I0 When 6 > 0, AEp/2 > 90.6/n mV, and the
voltammetric curve becomes broader and flatter. When 6 < 0,
Po
In-
PR
+ RT(
nF
- E - Eo') = I n f +
1 -f
AEp/2 90.6/n mV, giving a narrower and sharper peak.
Because 8* decreases in the presence of S , eq 16 predicts that
A E p / 2 will approach 90.6/n mV as 8s increases.
Square Wave Voltammetry. This method is more sensitive
where 6 = goo f gRR - 2gOR. than CVI5 and allows measurements at smaller adsorbate
Cyclic Voltammetry. For a single linear sweep in cyclic coverage. The theory of square wave voltammetry (SWV) for
+
voltammetry, where E = E, vt, Ei is the initial potential and surface-confined electroactive species was recently presented. l 6
Y is scan rate, eq 7 can be rewritten as However, to obtain interaction parameters, we need to consider
the Frumkin isotherm in developing an expression for the
current-potential curve. This was done by considering an
equivalent electrical circuit representing the experiment. An
"adsorption impedance" was included in parallel to the Warburg
From eq 11 we get the following equation for both the anodic impedance and double-layer capacitance. If diffusion is
and cathodic i-E curves negligible, the Warburg impedance can be removed, and the
SWV response for adsorbed reactants can be discussed in terms
of the equivalent circuit in Figure 1.
The parallel combination of the electrode double layer
capacitance, c d l , and the Faradaic pseudocapacitance, Cf,arising
Equation 13 predicts that the cathodic and anodic waves are from the attached reactant is in series with the uncompensated
symmetrical. It is identical to that for adsorption of a redox solution resistance, &.I4 This potential-dependent Faradaic
couple following the Frumkin isotherm when 8* = 1.I3-l4Peaks pseudocapacitance can be expressed as
are observed when f = 0.5. Anodic and cathodic peaks have
equal magnitudes

i = n2F3vr*
(6 > -4) Differentiation of eq 11 and substitution in eq
RT(8*6 + 4 )
which are directly proportional to potential scan rate. Peak
potentials are given by
16438 J. Phys. Chem., Vol. 99, No. 44, 1995
We further assume that during the life of each pulse the
change in total surface concentrations of R and 0 can be
ignored, and the Faradaic pseudocapacitance can be regarded
as constant. The current flowing in the circuit of Figure 1 can
be expressed as
where E,, is the magnitude of each potential pulse and z is the
time since its application.
Equation 20 predicts that for SWV at fixed z the largest
currents will result when Cf is largest. According to eqs 11
and 19, Cf will reach its maximum value when f = 0.5. The
SWV curves have peak potentials given by eq 15.
Anson et al.I4 showed that addition of extemal uncompensated
resistance led to significant increases in the sensitivity of
differential pulse voltammetry. As seen from eq 20, R, plays
the same role in SWV at a fixed sampling time. Differentiating
eq 20 with respect to R, leads to the prediction that the current
at a fixed sampling time will reach a maximum when R, is given
by
Substitution of eq 21 into eq 20 gives
We assume that the contribution of c d l to the SWV peak is
negligible, Le., c d ] << Cf. If we now define i as the Faradaic
current only, the current-potential curve on either the forward
or the reverse pulses of the SWV waveform is expressed by
combining eqs 19 and 22:
with peak current
n2$E,,r*
i =
2.718zRT(O*d + 4)
The half-peak width AEp12 is given by eq 16. The difference
between the currents on the forward and reverse pulses, a
familiar output mode for SWV, is given by multiplying eq 23
and eq 24 by 2.
The enhanced sensitivity of SWV for an adsorbed species
can be compared with CV by comparing their currents at
equivalent scan rates. Using the difference current output,
consider that v = f&, and z = l/2f0, where fo is the frequency
and E, is the staircase step height of the SWV. Then, from eqs
13 and 23
1.48E,,
i(SWV) = - i(CV) (25)
E,
For E,, = 25 mV and E, = 2 mV, SWV is about 18.5-fold
more sensitive than CV.
Peng and Rusling
Integration of eq 25 with respect to t gives
1.48E,,
Q(SWV) = - Q(W
E,
where Q(CV) is the integrated charge from the CV peak and
Q(SWV) is the integrated area under the SWV curve. Since
r*= Q(CV)/nF, we obtain
Equation 27 shows that r*is directly related to Q(SWV) and
the SWV parameters. This equation should allow SWV to be
used to estimate amounts of adsorbed species too small to be
measured by CV.
Experimental Section
Chemicals. Dimethyl(ferrocenylmethy1)hexadecyla"onium
(Fc-C16) bromide was synthesized as described previou~ly.~
Hexadecyltrimethylamonium bromide (cetyltrimethyl-
ammonium bromide, CTAB) was ACS reagent grade from
Aldrich. Water was distilled and then purified with a Sybron-
Barnstead Nanopure system to specific resistance > 15 M a - -
cm.
Apparatus and Procedures. CV and SWV employed a
PARC Model 273 Electrochemistry system and a cell with a
0.071 cm2 glassy carbon (GC) working electrode, a saturated
calomel (SCE) reference, and a platinum counter electrode. The
GC surface was ground initially on 240 grit Sic paper, and then
polished on billiard cloth with successive aqueous suspensions
of 6, 1,0.3, and 0.05 pm alumina, followed by 1 min ultrasonic
cleaning in pure water after each step.I9 Between replicate
experiments, polishing with 0.3 and 0.05 pm alumina and
ultrasonic cleaning were used.
For voltammetry, freshly polished electrodes were soaked in
adsorbate solutions for an appropriate time to attain saturation
coverage and then transferred to adsorbate-free electrolyte
solutions where voltammetry was performed immediately.
Adsorption time was generally 3 h in 25 pM solutions and '8
h in submicromolar solutions. Oxygen was removed from
solutions by purging with purified nitrogen for 220 min. All
experiments were done at 25 k 1 "C. Analyses of data by
nonlinear regression were done with a general program employ-
ing the Marquardt-Levenberg algorithm.20
Results
Cyclic Voltammetry. The alkylammonium ferrocene am-
phiphile Fc-C 16 adsorbs relatively strongly on GC electrode^.^
After 1-2 h in the Fc-C16 solution, voltammograms of
electrodes transferred to surfactant-free 0.2 M NaCl showed no
loss in peak current for several cycles.
Figure 2 shows background corrected CVs of adsorbed Fc-
C16 in 0.2 M NaC1. They correspond to films obtained by
soaking GC electrodes in 25 pM Fc-C16 for 5 s to 1.5 h (Table
1). The area under the anodic peak was integrated to obtain
the electrical charge passed to oxidize the ferrocene group. For
electrodes soaked in adsorbate solutions for equal times, peak
currents (ip) for the oxidation of Fc-C16 were linear with scan
rate in the range 20-200 mV s-l, as predicted by eq 14.
The largest set of peaks in Figure 2 were obtained after 1.5
h storage of the electrode in 25 pM Fc-C16. Increases of
adsorption time up to 24 h in this solution showed no increase
in the peak currents. Previous studies5 suggest that this CV
represents saturation coverage of the electrode with Fc-C16.
Surfactants Coadsorbed on Electrodes .IPhys.
. Chem., Vol. 99, No. 44, 1995 16439
1.50 I I 1.60

1.20 1 n

.-2 0.80 1
-0.50
0.40 1 f
-1 .oo

-1.50'
0.15
' '
0.25
' '
0.35
' '
0.45
' '
0.55
' '
0.65
' '
0.75
0.00
0.15
1
0.25 0.35 0.45 0.55 0.65 0.75

E , V vs. SCE E, V vs. SCE

Figure 2. Background-subtracted CVs at 100 mV s-l for Fc-C16 Figure 4. A comparison of experimental (-) and theoretical ( 0 )
adsorbed onto GC electrodes. The electrode was soaked in 25 pM oxidation branches of CVs at 100 mV s-' for a saturation coverage of
Fc-C16 solution (0.2 M NaCl) for 5 s, 30 s, 5 min, and 1.5 h. Peak Fc-C16 on GC electrode in 0.2 M NaCl. Theoretical voltammogram
currents increase with adsorption time. computed by nonlinear regression onto eqs 13 and 28, using 6 and a
background offset as regression parameters.*la
TABLE 1. Parameters from CV for Fc-C16 Adsorbed on
GC Electrodes 61 1
t 1
CVno. P Eo (mV)b hE,~z(mV)~ Q e C ) 0
1 5s 490 123.3 1.005 0.448
2 30 s 506 136.7 1.688 0.752
3 5 min 513 138.3 2.010 0.896
4 1.5 h 522 156.7 2.244 1.000
Adsorption time in 25 pM Fc-C16/0.2M NaCl solution. Obtained
at 100 mVS K I vs SCE.
2I
1

Y
520
510

500
x
1
0""""""""""'
0 100 200 300

ReSi8t"ICe added (Ohms)

400

$ 490 1 , Figure 5. Influence of added resistance in the measuring circuit on

SWV peak currents for full-coverage of Fc-C16 on GC electrode in
0.2 M NaC1. E,, = 25 mV, E, = 2 mV, fo = 50 Hz. The
uncompensated resistance in the cell was 500 Q.
460

450
t achieved. The cell had a measured uncompensated resistance
0.00 0.20 0.40 0.60 0.80
Fractional coverage
Figure 3. Influence of f?* on Ep at 100 mV s-I for adsorbed Fc-C16
on GC electrodes.
The corrected area under the oxidation peak is 2.244 pC,
corresponding to a surface concentration of 3.28 x
mol cm-*, and an area of 49 A2/molecule. The ferrocene head
group in Fc-C16 has a cross-sectional area7a of 50 f 5 A2.
Monolayer coverage with head-down orientation is implied, in
accord with our previous result^.^ The saturation adsorption is
thus considered to be at full coverage, i.e., 8* = 1.
Table 1 presents Ep, AEp12, and 8* for Fc-C16 on GC. All
AEp/2values for the one-electron Fc-C16 oxidation are larger
than 90.6 mV, suggesting strong interactions between adsorbed
molecules. A plot of Ep vs 8* (Figure 3), according to eq 15,
gives a value of 3.54 for goo - gRR.
Substituting eq 15 in eq 11, we obtain
E - E = - ln-
p 3 If-f
+ cf- 0.5)@*6]
Figure 4 shows an experimental CV and its fit by nonlinear
regression onto eqs 13 and 28.*Ia This fit gave 6 = 2.66 f
0.09. Relatively good agreement between the experimental and
theoretical curves shows that the Frumkin isotherm represents
the adsorption behavior well.
Square Wave Voltammetry. As discussed above, there is
an optimum resistance for SWV where maximum currents are
1.00 of 500 Q. Figure 5 shows that at uncompensated resistance
(R,) of 600 S2, Le., with an added R, of 100 S2, the current for
Fc-C16 at full-coverage reaches a maximum. The optimum
resistance was included in the measuring circuit for each
additional experiment.
SWV was done for Fc-C16 films on GC at saturation
coverage. In order to compare the SWV results to CV, we chose
E,, = 2 mV andfo = 50 Hz so that the effective Y = 100
mV s-l, as used for CV. SWV curves (Figure 6) gave Ep =
519 mV vs SCE, AEp,2 = 155 mV, which compare favorably
with those from CV (cf. Table 1). Integration of the area under
the curve gave a charge Q(SWV) of 41.5 pC. From eq 26, the
theoretical Q(SWV) computed from Q(CV) is 41.0 pC. Thus,
good agreement between SWV and CV was obtained.
By using the value of 8* obtained from the saturation
coverage CV in Figure 2, the SWV curve was fit onto eqs 23
and 28.21aAs shown in Figure 6, good agreement is achieved.
The fitting gave 6 = 2.54 f 0.06, which is very close to the
value of 2.66 obtained by CV.
SWV is advantageous for low coverage of electroactive
(28) adsorbate, as illustrated by a comparison (Figure 7). Prepared
by using a 1:lO mixture of Fc-C16 and nonelectroactive
surfactant CTAB, the GC surfaces contained only a small frac-
tion of Fc-C16. The background current in CV is so large that
the oxidation and reduction waves are nearly imperceptible. The
SWV response for the same electrode, shows a well-resolved
peak, allowing accurate estimation of required parameters.
Adsorption Isotherms. In order to find all the interaction
parameters, it is necessary to obtain g R R . Adsorption isotherms
16440 J. Phys. Chem., Vol. 99, No. 44, 1995 Peng and Rusling

6 r I 40 1
t I
30
4

%
0
20

10

0' " " ' I " " ' I 0 " ' " ' I " '

0.15 0.25 0.35 0.45 0.55 0.65 0.75 0.00 0.20 0.40 0.60 0.80 1.00

E, V va. SCE (CM)

Figure 6. Comparison of experimental
curves for a saturation coverage of Fc-C16 on GC electrode in 0.2 M
NaCl. The experimental SWV was obtained with E,, = 25 mV, E, =
2 mV, fa = 50 Hz and R, = 600 Q. The theoretical curve was
calculated by nonlinear regression onto eqs 23 and 28 using 6 and a
background offset as regression parameters.*Ia
(-) and theoretical (0)SWV
CPC.C,,
Figure 8. Adsorption isotherm for Fc-C16 on GC obtained by SWV.
Each point was measured after overnight soaking on a freshly polished
GC electrode in Fc-C16 solutions (0.2 M NaC1). E,, = 25 mV, E, =
2 mV, andfo = 50 Hz. Solid line is the best fit of eq 1 by nonlinear
regression.

2.00 1

where K = /?R/&.
.- The surface coverage of Fc-C16 can be controlled by
+
changing the ratio [Fc-C16]/([Fc-C16] [CTAB]) in solution.
+
The total concentration [Fc-C16] [CTAB] was kept at 25
pM, and the ratios of the two species were varied.*Ib The fit
-1.00' ' ' ' ' ' ' " ' ' ' I
0.15 0.35 0.55 0.75 of the adsorption isotherm for Fc-C16 in the presence of CTAB
(Figure 9) onto eq 31 gave K = 1.39 f 0.36 M-', gRS - gss =
E, V va. SCE
+
0.13 f 0.04, gRR - 2 g ~ s gss = -0.69 f 0.12. Thus, gRS =
-1.90 and gss = -2.03.

0.50
OAO m Characteristic potentials of SWVs were examined over a
range of Fc-C16 coverage. AEp/2 increases from 107.9 mV at
8* = 0.03 to 147.9 mV at 8* = 0.83, in accord with predictions
based on eq 16. Also, a negative shift was observed in the

-
.- peak potential Ep. The Epvs 8* plot (Figure 10) has a slope of
0.20 I / \ I -21.8 mV and an intercept of 537.9 mV. From eq 15 we find
gos - gRS = 2.62, and gos = 0.72.

0.00
0.15 0.35
E, V
Figure 7. Voltammograms obtained by (a) CV at 100 mV s-' and (b)
SWV (Es, = 25 mV, E, = 2 mV,fa = 50 Hz, and R, = 3 kQ) in 0.2
M NaC1. GC electrodes were soaked in 1.0 pM Fc-C16 + 10 pM
CTAB + 0.2 M NaCl solution to obtain saturation coverage.
were constructed for this purpose by measuring Q(SWV) for
Fc-C16. The fit of experimental data onto the Frumkin isotherm
(Figure 8) gave gRR = -2.46 f 0.31 and PR = 3.04 k 0.59
M-'. Therefore, by using 6 and the average goo - gRR, we
find that goo = 1.08 and goR = -1.99.
The Frumkin isotherm for coadsorption of two species (R,
S) on a solid surface can be expressed as
+
If CR CSis so large that the total surface concentrations of R
+
and S approach Tm,i.e., if 8 R 8s is approximately 1, dividing
eq 29 by eq 30 gives
Discussion
0.55 0.75
By combining voltammetry and adsorption isotherms for
VO. SCE electroactive and nonelectroactive coadsorbates, methods de-
scribed herein provided interaction parameters between all the
amphiphilic species adsorbed on the electrode. In the system
studied, Fc-C16 is adsorbed more strongly than CTAB, as
suggested by Figure 9 and the K = PR//?s = 1.39 derived from
it. Thus, at a given ratio of [Fc-C16]/[CTAB], proportionally
more Fc-C16 adsorbed onto the GC electrode.
The interaction parameters are collected in Table 2. Param-
eters gRR, goR, gRS, and gss are all negative, suggesting attractive
intermolecular interactions for Fc-C16 with itself, Fc-C16 with
its oxidized form, Fc-C16 and CTAB, and CTAB with itself.
The stability of Langmuir-Blodgett monolayers at the electrode/
electrolyte interface has been suggested to derive from cohesive
hydrophobic interactions between adjacent hydrocarbon tails.22
Similarly, our previous work on adsorption of ferrocene
surfactants of different chain lengths on PG suggested a
substantial hydrophobic driving force for the ad~orption,~ which
has also been proposed for other adsorbed amphiphiles on
electrodes3 Thus, it is reasonable to infer that in the closely
packed monolayers studied here, hydrophobic interactions are
the source of attractive forces.
Positive values of goo and gos suggest repulsive interactions
between oxidized Fc-C16 with itself and with CTAB. This
probably arises because repulsion of the doubly positive head
Surfactants Coadsorbed on Electrodes
2 1.00 I I
0.00 0.20 0.40 0 . 6 0 0.80 1.00
[Fc-C~~]/([FC-C~~)+[CTAB])
Figure 9. Adsorption isotherm obtained from SWV for Fc-C16
coadsorbed with CTAB on GC electrodes in 0.2 M NaC1, where
[Fc-C16] + [CTAB] = 25 pM. E,, = 25 mV, E, = 2 mV, andfo =
50 Hz. Solid line is the best fit of eq 31 by nonlinear regression.
r------
560
500
0.00 0.20 0.40 0 . 6 0 0.80 1.00
Fract. Coverage of F c - C l 6
Figure 10. Peak potentials of SWVs vs fractional coverage for Fc-
C16 coadsorbed with CTAB on GC electrodes in 0.2 M NaCI.
Conditions as in Figure 9.
TABLE 2. Intermolecular Interaction Parameters in 0.2 M
NaCIa
goo gOR gRR gos gRS
1.08 -1.99 -2.46 0.72 -1.90
Subscripts are 0 = oxidized form of Fc-CI6, R = reduced form
of Fc-C16, S = CTAB. Relative standard errors estimated from the
regression analyses are within f 1 5 % .
group of oxidized Fc-C16 with other positive head groups
overcomes the hydrophobic attraction. Parameter values in the
order goo > gOR > gRR may be attributed to the balance between
hydrophobic attraction and Coulombic repulsion involving the
doubly charged head group of oxidized Fc-C16. These results
are also in agreement with the view that Coulombic repulsion
is responsible for the disruption of aqueous micelles of dodecyl-
(ferrocenylmethy1)dimethyla"onium ion upon oxidation.23
The relation gRR < gss suggests that hydrophobic interactions
are slightly larger for Fc-C16/Fc-C16 than for CTABKTAB,
and Fc-C16 is more strongly adsorbed than CTAB. These two
species both have C16 alkyl chains, but Fc-C16 has the
hydrophobic ferrocenylmethyl group. Results suggest that a
stronger hydrophobic driving force for adsorption leads to a
favorable competition of Fc-C16 with CTAB for sites on the
electrode surface.
Although it is not possible to unambiguously interpret our
results on a detailed molecular level, they are consistent with a
model in which Fc-C16 adsorbate molecules are distributed with
CTAB on the hydrophilic GC surface in a head-down orienta-
J. Phys. Chem., Vol. 99, No. 44, 1995 16441
tion. This was previously found for Fc-C16 on GC5and metal'
electrodes and is consistent with head group down orientations
of cationic surfactants on hydrophilic surfaces confirmed by
spectroscopic methods3 The different Coulombic and hydro-
phobic interactions between the various coadsorbates may
'
influence the supramolecular structures of adsorbed films
containing these species.
Bilayer coverage of the GC electrode in the 25 pM adsorbate
solutions cannot be ruled out. Monolayers of CTA+ ions on
mica began to develop a partial second adsorbed layer in 1-2
days in 6-8 pM solutions.24 At the 25 pM concentrations used
in our work, such bilayer development may be faster. However,
a second layer of Fc-C16 head groups facing the solution would
be too far away from the electrode to accept electrons ef-
f i ~ i e n t l yand
~ ~are probably electrochemically invisible.
Acknowledgment. The authors are grateful for financial
support of this work by a grant from the National Science
Foundation (CTS-9306961).
References and Notes
(1) Friberg, S. Adu. Colloid Interface Sci. 1990, 32, 167.
(2) Rusling, J. F. Acc. Chem. Res. 1991, 24, 75.
(3) Rusling, J. F. In Electroanalytical Chemistry; Bard, A. J., Ed.;
Marcel Dekker: New York, 1994; Vol. 19, pp 1-88.
(4) Rusling, J. F. In Modern Aspects of Electrochemistry; Conway, B.
E., Bockris, J. O'M., Eds.; Plenum Press, New York, 1994; No. 26, pp
49-104. b
( 5 ) Peng, W.; Zhou, D.; Rusling, J. F. J . Phys. Chem. 1995, 99, 6986.
(6) Adamson, A. W. Physical Chemistry of Surfaces, 5th ed.; Wiley:
New York, 1990.
(7) (a) Donohue, J. J.; Buttry, D. A. Langmuir 1989, 5, 671. (b)
Nordyke, L. L.; Buttry, D. A. Langmuir 1991, 7, 380.
(8) Delong, H. C.; Donohue, J. J.; Buttry, D. A. Langmuir 1991, 7,
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eqs 13 and 23. A constant offset background parameter was added to eqs
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C16 for CTAB on the surface was observed.
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