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

We further assume that during the life of each pulse the Integration of eq 25 with respect to t gives
change in total surface concentrations of R and 0 can be
ignored, and the Faradaic pseudocapacitance can be regarded 1.48E,,
as constant. The current flowing in the circuit of Figure 1 can Q(SWV) = - Q(W
E,
be expressed as
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
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 Equation 27 shows that r*is directly related to Q(SWV) and
currents will result when Cf is largest. According to eqs 11 the SWV parameters. This equation should allow SWV to be
and 19, Cf will reach its maximum value when f = 0.5. The used to estimate amounts of adsorbed species too small to be
SWV curves have peak potentials given by eq 15. measured by CV.
Anson et al.I4 showed that addition of extemal uncompensated
resistance led to significant increases in the sensitivity of Experimental Section
differential pulse voltammetry. As seen from eq 20, R, plays Chemicals. Dimethyl(ferrocenylmethy1)hexadecyla"onium
the same role in SWV at a fixed sampling time. Differentiating (Fc-C16) bromide was synthesized as described previou~ly.~
eq 20 with respect to R, leads to the prediction that the current Hexadecyltrimethylamonium bromide (cetyltrimethyl-
at a fixed sampling time will reach a maximum when R, is given ammonium bromide, CTAB) was ACS reagent grade from
by 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
Substitution of eq 21 into eq 20 gives 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
We assume that the contribution of c d l to the SWV peak is experiments, polishing with 0.3 and 0.05 pm alumina and
negligible, Le., c d ] << Cf. If we now define i as the Faradaic ultrasonic cleaning were used.
current only, the current-potential curve on either the forward For voltammetry, freshly polished electrodes were soaked in
or the reverse pulses of the SWV waveform is expressed by adsorbate solutions for an appropriate time to attain saturation
combining eqs 19 and 22: 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
with peak current nonlinear regression were done with a general program employ-
ing the Marquardt-Levenberg algorithm.20
n2$E,,r*
i =
2.718zRT(O*d + 4) Results
Cyclic Voltammetry. The alkylammonium ferrocene am-
The half-peak width AEp12 is given by eq 16. The difference phiphile Fc-C 16 adsorbs relatively strongly on GC electrode^.^
between the currents on the forward and reverse pulses, a After 1-2 h in the Fc-C16 solution, voltammograms of
familiar output mode for SWV, is given by multiplying eq 23 electrodes transferred to surfactant-free 0.2 M NaCl showed no
and eq 24 by 2. loss in peak current for several cycles.
The enhanced sensitivity of SWV for an adsorbed species Figure 2 shows background corrected CVs of adsorbed Fc-
can be compared with CV by comparing their currents at C16 in 0.2 M NaC1. They correspond to films obtained by
equivalent scan rates. Using the difference current output, soaking GC electrodes in 25 pM Fc-C16 for 5 s to 1.5 h (Table
consider that v = f&, and z = l/2f0, where fo is the frequency 1). The area under the anodic peak was integrated to obtain
and E, is the staircase step height of the SWV. Then, from eqs the electrical charge passed to oxidize the ferrocene group. For
13 and 23 electrodes soaked in adsorbate solutions for equal times, peak
currents (ip) for the oxidation of Fc-C16 were linear with scan
1.48E,, rate in the range 20-200 mV s-l, as predicted by eq 14.
i(SWV) = - i(CV) (25) The largest set of peaks in Figure 2 were obtained after 1.5
E, h storage of the electrode in 25 pM Fc-C16. Increases of
adsorption time up to 24 h in this solution showed no increase
For E,, = 25 mV and E, = 2 mV, SWV is about 18.5-fold in the peak currents. Previous studies5 suggest that this CV
more sensitive than 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 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
Fractional coverage Fc-C16 at full-coverage reaches a maximum. The optimum
Figure 3. Influence of f?* on Ep at 100 mV s-I for adsorbed Fc-C16 resistance was included in the measuring circuit for each
on GC electrodes. additional experiment.
SWV was done for Fc-C16 films on GC at saturation
The corrected area under the oxidation peak is 2.244 pC, coverage. In order to compare the SWV results to CV, we chose
corresponding to a surface concentration of 3.28 x E,, = 2 mV andfo = 50 Hz so that the effective Y = 100
mol cm-*, and an area of 49 A2/molecule. The ferrocene head mV s-l, as used for CV. SWV curves (Figure 6) gave Ep =
group in Fc-C16 has a cross-sectional area7a of 50 f 5 A2. 519 mV vs SCE, AEp,2 = 155 mV, which compare favorably
Monolayer coverage with head-down orientation is implied, in with those from CV (cf. Table 1). Integration of the area under
accord with our previous result^.^ The saturation adsorption is the curve gave a charge Q(SWV) of 41.5 pC. From eq 26, the
thus considered to be at full coverage, i.e., 8* = 1. theoretical Q(SWV) computed from Q(CV) is 41.0 pC. Thus,
Table 1 presents Ep, AEp12, and 8* for Fc-C16 on GC. All good agreement between SWV and CV was obtained.
AEp/2values for the one-electron Fc-C16 oxidation are larger By using the value of 8* obtained from the saturation
than 90.6 mV, suggesting strong interactions between adsorbed coverage CV in Figure 2, the SWV curve was fit onto eqs 23
molecules. A plot of Ep vs 8* (Figure 3), according to eq 15, and 28.21aAs shown in Figure 6, good agreement is achieved.
gives a value of 3.54 for goo - gRR. The fitting gave 6 = 2.54 f 0.06, which is very close to the
Substituting eq 15 in eq 11, we obtain value of 2.66 obtained by CV.
SWV is advantageous for low coverage of electroactive
E - E = - ln-
p 3 If-f
+ cf- 0.5)@*6] (28) adsorbate, as illustrated by a comparison (Figure 7). Prepared
by using a 1:lO mixture of Fc-C16 and nonelectroactive
Figure 4 shows an experimental CV and its fit by nonlinear surfactant CTAB, the GC surfaces contained only a small frac-
regression onto eqs 13 and 28.*Ia This fit gave 6 = 2.66 f tion of Fc-C16. The background current in CV is so large that
0.09. Relatively good agreement between the experimental and the oxidation and reduction waves are nearly imperceptible. The
theoretical curves shows that the Frumkin isotherm represents SWV response for the same electrode, shows a well-resolved
the adsorption behavior well. peak, allowing accurate estimation of required parameters.
Square Wave Voltammetry. As discussed above, there is Adsorption Isotherms. In order to find all the interaction
an optimum resistance for SWV where maximum currents are 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)


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

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 Discussion
0.15 0.35 0.55 0.75
By combining voltammetry and adsorption isotherms for
E, V VO. SCE electroactive and nonelectroactive coadsorbates, methods de-
Figure 7. Voltammograms obtained by (a) CV at 100 mV s-' and (b) scribed herein provided interaction parameters between all the
SWV (Es, = 25 mV, E, = 2 mV,fa = 50 Hz, and R, = 3 kQ) in 0.2 amphiphilic species adsorbed on the electrode. In the system
M NaC1. GC electrodes were soaked in 1.0 pM Fc-C16 + 10 pM studied, Fc-C16 is adsorbed more strongly than CTAB, as
CTAB + 0.2 M NaCl solution to obtain saturation coverage.
suggested by Figure 9 and the K = PR//?s = 1.39 derived from
it. Thus, at a given ratio of [Fc-C16]/[CTAB], proportionally
were constructed for this purpose by measuring Q(SWV) for more Fc-C16 adsorbed onto the GC electrode.
Fc-C16. The fit of experimental data onto the Frumkin isotherm The interaction parameters are collected in Table 2. Param-
(Figure 8) gave gRR = -2.46 f 0.31 and PR = 3.04 k 0.59 eters gRR, goR, gRS, and gss are all negative, suggesting attractive
M-'. Therefore, by using 6 and the average goo - gRR, we intermolecular interactions for Fc-C16 with itself, Fc-C16 with
find that goo = 1.08 and goR = -1.99. its oxidized form, Fc-C16 and CTAB, and CTAB with itself.
The Frumkin isotherm for coadsorption of two species (R, The stability of Langmuir-Blodgett monolayers at the electrode/
S) on a solid surface can be expressed as 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.
+
If CR CSis so large that the total surface concentrations of R Positive values of goo and gos suggest repulsive interactions
+
and S approach Tm,i.e., if 8 R 8s is approximately 1, dividing between oxidized Fc-C16 with itself and with CTAB. This
eq 29 by eq 30 gives probably arises because repulsion of the doubly positive head
Surfactants Coadsorbed on Electrodes J. Phys. Chem., Vol. 99, No. 44, 1995 16441

2 1.00 I I 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
0.00 0.20 0.40 0 . 6 0 0.80 1.00 days in 6-8 pM solutions.24 At the 25 pM concentrations used
[Fc-C~~]/([FC-C~~)+[CTAB]) in our work, such bilayer development may be faster. However,
a second layer of Fc-C16 head groups facing the solution would
Figure 9. Adsorption isotherm obtained from SWV for Fc-C16
coadsorbed with CTAB on GC electrodes in 0.2 M NaC1, where be too far away from the electrode to accept electrons ef-
[Fc-C16] + [CTAB] = 25 pM. E,, = 25 mV, E, = 2 mV, andfo = f i ~ i e n t l yand
~ ~are probably electrochemically invisible.
50 Hz. Solid line is the best fit of eq 31 by nonlinear regression.

r------
Acknowledgment. The authors are grateful for financial
support of this work by a grant from the National Science
560 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
500 49-104. b
0.00 0.20 0.40 0 . 6 0 0.80 1.00 ( 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:
Fract. Coverage of F c - C l 6 New York, 1990.
Figure 10. Peak potentials of SWVs vs fractional coverage for Fc- (7) (a) Donohue, J. J.; Buttry, D. A. Langmuir 1989, 5, 671. (b)
Nordyke, L. L.; Buttry, D. A. Langmuir 1991, 7, 380.
C16 coadsorbed with CTAB on GC electrodes in 0.2 M NaCI. (8) Delong, H. C.; Donohue, J. J.; Buttry, D. A. Langmuir 1991, 7,
Conditions as in Figure 9. 2196.
(9) Facci, J. S. Langmuir 1987, 3, 525.
TABLE 2. Intermolecular Interaction Parameters in 0.2 M (IO) Bard, A. J.; Faulkner, L. R. Electrochemical Methods; Wiley: New
NaCIa York, 1980; Chapter 12.
(11) Parry, J. M.; Parsons, R. J . Electrochem. SOC. 1966, 113, 992.
goo gOR gRR gos gRS gss (12) Damaskin, B. B.; Petrii, 0. A,; Batrakov, V. V. Adsorption of
1.08 -1.99 -2.46 0.72 -1.90 -2.03 Organic Compounds on Electrodes; Plenum: New York, 1971; pp 76-
134.
Subscripts are 0 = oxidized form of Fc-CI6, R = reduced form (13) Laviron, E. J . Electroanal. Chem. 1974, 52, 395.
of Fc-C16, S = CTAB. Relative standard errors estimated from the (14) Brown, A. P.; Anson, F. C. Anal. Chem. 1977, 49, 1589.
regression analyses are within f 1 5 % . (15) Osteryoung, J.; O'Dea, J. J. Electroanalytical Chemistry;Bard, A.
J., Ed.; Marcel Dekker: New York, 1986; Vol. 14, pp 209-308.
group of oxidized Fc-C16 with other positive head groups (16) O'Dea, J. J.; Osteryoung, J. Anal. Chem. 1993, 65, 3090-3097.
overcomes the hydrophobic attraction. Parameter values in the (17) Delahay, P.; Holub, K. J. Electroanal. Chem. 1968, 16, 131.
(18) Timmer, B.; Sluyters-Rehbach, M.; Sluyters, J. H. J . Electroanal.
order goo > gOR > gRR may be attributed to the balance between Chem. 1968, 18, 93.
hydrophobic attraction and Coulombic repulsion involving the (19) Kamau, G. N.; Willis, W. S.; Rusling, J. F. Anal. Chem. 1985,57,
doubly charged head group of oxidized Fc-C16. These results 545.
(20) Rusling, J. F. CRC Crit. Rev. Anal. Chem. 1989, 21, 49.
are also in agreement with the view that Coulombic repulsion (21) (a) Equation 28 was solved by a numerical subroutine to provide
is responsible for the disruption of aqueous micelles of dodecyl- appropriate values o f f between 0 and 1 to be used during regression onto
(ferrocenylmethy1)dimethyla"onium ion upon oxidation.23 eqs 13 and 23. A constant offset background parameter was added to eqs
The relation gRR < gss suggests that hydrophobic interactions 13 and 23 and was determined in the regression analyses.I5 (b) Films were
prepared by soaking GC electrodes in the 25 pM solutions for 3 h.
are slightly larger for Fc-C16/Fc-C16 than for CTABKTAB, However, after several days of soaking a small amount of exchange of Fc-
and Fc-C16 is more strongly adsorbed than CTAB. These two C16 for CTAB on the surface was observed.
species both have C16 alkyl chains, but Fc-C16 has the (22) (a) Facci, J. S.; Falcigno, P. A.; Gold, J. M. Langmuir 1986, 2,
132. (b) Facci, J. S. In Molecular Design of Electrode Surfaces, Techniques
hydrophobic ferrocenylmethyl group. Results suggest that a of Chemistry; Murray, R. W., Ed.; Wiley: New York, 1992; Vol. 22, pp
stronger hydrophobic driving force for adsorption leads to a 119-158.
favorable competition of Fc-C16 with CTAB for sites on the (23) Saji, T.; Hoshino, K.; Aoyagui, S. J . Am. Chem. SOC.1985, 107,
6865.
electrode surface. (24) Kekicheff, H. K.; Christenson, H. K.; Ninham, B. W. Colloids Surf.
Although it is not possible to unambiguously interpret our 1989, 40, 31.
results on a detailed molecular level, they are consistent with a (25) (a) Widrig, C. A.; Majda, M. Langmuir 1989, 5, 689. (b) Zhang,
model in which Fc-C16 adsorbate molecules are distributed with X.; Bard, A. J. J . Am. Chem. SOC. 1989, 111, 8098.
CTAB on the hydrophilic GC surface in a head-down orienta- JP95 18944