1995,99, 1643616441
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 (FcC16) adsorbed onto glassy carbon
electrodes from aqueous solutions containing hexadecyltrimethylamonium bromide (CTAB). Results were
consistent with headdown orientations of these surfactants on a glassy carbon electrode. While mixed adsorbate
layers were formed, a small preference for adsorption of FcC16 was found in the presence of CTAB.
Interaction parameters between FcC 164%C 16, FcC 16/CTAB, reduced and oxidized forms of FcC 16, and
CTAB/CTAB were attractive, suggesting favorable hydrophobic interactions. Interactions of the +2 charged,
oxidized FcC 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.' Surfactantbased 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
headdown 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 nelectron 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
0022365419512099 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
80 + 8 R = 8* (10)
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 (FcC16) 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 currentpotential 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 adsorbatefree 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 MarquardtLevenberg algorithm.20
n2$E,,r*
i =
2.718zRT(O*d + 4) Results
Cyclic Voltammetry. The alkylammonium ferrocene am
The halfpeak width AEp12 is given by eq 16. The difference phiphile FcC 16 adsorbs relatively strongly on GC electrode^.^
between the currents on the forward and reverse pulses, a After 12 h in the FcC16 solution, voltammograms of
familiar output mode for SWV, is given by multiplying eq 23 electrodes transferred to surfactantfree 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 FcC16 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 FcC16 were linear with scan
1.48E,, rate in the range 20200 mV sl, 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 FcC16. 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 18.5fold in the peak currents. Previous studies5 suggest that this CV
more sensitive than CV. represents saturation coverage of the electrode with FcC16.
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
Y
520
510
500
x
1
0""""""""""'
0 100 200 300
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 FcC16 at fullcoverage reaches a maximum. The optimum
Figure 3. Influence of f?* on Ep at 100 mV sI for adsorbed FcC16 resistance was included in the measuring circuit for each
on GC electrodes. additional experiment.
SWV was done for FcC16 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 sl, as used for CV. SWV curves (Figure 6) gave Ep =
group in FcC16 has a crosssectional area7a of 50 f 5 A2. 519 mV vs SCE, AEp,2 = 155 mV, which compare favorably
Monolayer coverage with headdown 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 FcC16 on GC. All good agreement between SWV and CV was obtained.
AEp/2values for the oneelectron FcC16 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 Iff
+ cf 0.5)@*6] (28) adsorbate, as illustrated by a comparison (Figure 7). Prepared
by using a 1:lO mixture of FcC16 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 FcC16. 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 wellresolved
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
2.00 1
where K = /?R/&.
. The surface coverage of FcC16 can be controlled by
+
changing the ratio [FcC16]/([FcC16] [CTAB]) in solution.
+
The total concentration [FcC16] [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 FcC16 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 FcC16 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 FcC16 + 10 pM studied, FcC16 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 [FcC16]/[CTAB], proportionally
were constructed for this purpose by measuring Q(SWV) for more FcC16 adsorbed onto the GC electrode.
FcC16. 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 FcC16 with itself, FcC16 with
find that goo = 1.08 and goR = 1.99. its oxidized form, FcC16 and CTAB, and CTAB with itself.
The Frumkin isotherm for coadsorption of two species (R, The stability of LangmuirBlodgett 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 FcC16 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 FcC16 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
'
r
Acknowledgment. The authors are grateful for financial
support of this work by a grant from the National Science
560 Foundation (CTS9306961).