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Mikrochim.

Acta 106, 287-292 (1992) Mikrochimica


Acta
9 by Springer-Verlag1992
Printed in Austria

The Effect of Surfactants on the


pH Transition Interval of Bromothymol Blue
Immobilized on XAD 4

David C. Ashworth and Ramaier Narayanaswamy*


Department of Instrumentation and Analytical Science,U.M.I.S.T., P.O. Box 88, Manchester,
M60 1QD, United Kingdom

Abstract. Cationic, anionic and non-ionic surfactants adsorb readily from


aqueous solution on to Amberlite XAD 4. The ionic surfactants cause the pH
of the solution in contact with the resin to differ from that in the bulk of solution,
cationic surfactants increasing the interfacial pH and anionic surfactants de-
creasing it. This causes a shift in the pH transition interval of a co-adsorbed pH
indicator when measured with respect to the bulk solution. The quantity of ionic
surfactant adsorbed tends to a constant value (presumably monolayer coverage)
with increasing solution concentration, this amount being a function of the
individual surfactant, whereas non-ionic surfactants readily form multilayers.
Significant adsorption occurs when the surfactant possesses at least 14 carbon
atoms.
Keywords: surfactants, immobilized reagents, dissociated constant, optical fibre,
reflectometry.

During the last ten years the technique of optical fibre chemical sensing, using
immobilized reagents, has grown steadily in importance, as testified by a number of
reviews on the subject [1-4]. Several workers have used the facile immobilization
technique of adsorption from solution on to a polymeric matrix [5-8], such as
Amberlite XAD 4 (microporous cross-linked polystyrene). However care has to be
exercised in the determination of analytes in aqueous solution using this reagent
phase as the substrate is non-selective in its adsorptive properties and may well
co-adsorb adventitious organic matter, possibly influencing the response of the
reagent.

The adsorption of surfactants on to substrates has been extensively studied, and


various adsorption isotherms have been reported [9-11]. It is generally accepted

* To whom correspondenceshould be addressed


288 D.C. Ashworth and R. Narayanaswamy

that a two-step adsorption mechanism operates, substrate-surfactant interaction


leading to adsorption followed by association of the hydrocarbon chains to give a
hemimicelle. Recently an equation has been derived which interprets the various
types of surfactant adsorption isotherms [12]. It has been shown that adsorption
of sodium lauryl sulphate on polystyrene latex particles follows a Langmuir iso-
therm [13]. The competitive adsorption of an anionic and a non-ionic surfactants
on polystyrene latex resulted in the non-ionic surfactants adsorbing in excess on the
latex surface [14].
Whilst much work has been done on surfactant adsorption isotherms the effect
of an adsorbed surfactant on a co-adsorbed reagent has been only briefly reported
[ 15], following the observation that whereas tetramethylammonium hydroxide had
no effect on the pKa ofa chromogenic crown ether, tetrabutylammonium hydroxide
lowered the pKa by about two pH units. It was of interest to study this effect further,
and we report here the influence of cationic, anionic and non-ionic surfactants
adsorbed on XAD 4 on the pH transition interval of co-adsorbed bromothymol
blue. The term "surfactant" is used in this paper to denote an interface-active agent.

Experimental
The experiments were conducted in a flowcell interfaced to appropriate instrumentation by means of
optical fibres, as decribed elsewhere [16]. The reservoir solution and the Amberlite XAD 4 (B.D.H.
Ltd. 90 120 #m) were prepared as previously described [17] prior to use.
The adsorption of bromothymol blue on to XAD 4 was carried out from methanolic solution
(0.1% m/v). The flow cell was charged with the dyed resin and a reflectance versus pH curve was
obtained as previously described [-15]. To another reservoir solution was added sufficient surfactant
to give a concentration of 5.6 x 10-5 M and the solution was pumped through the flowcell for 24 h.
A reflectance versus pH curve was then obtained at a fixed wavelength of 600 nm. This was repeated
with surfactant concentrations of 2.8 x 10-4 M and 5.6 x 10-4 M. A fresh sample of dyed resin was
used with each new surfactant.
Tetraalkylammonium bromides (Aldrich, alkyl = methyl, ethyl, butyl, hexyl, octyl), cetylpyridi-
nium chloride and Triton X 100 (polyethoxylated (d.p. = 10) octylphenol) (B.D.H. Ltd.), and sodium
dodecylbenzenesulphonate (Aldrich) were used as received.

Results and Discussion


The reflectance versus pH relationship of bromothymol blue on XAD 4 was ex-
amined in the absence and presence (2.8 x 10 -4 M) of the cationic surfactant
tetrabutylammonium bromide (Fig. 1). The pKa of the indicator was calculated in
each case using the Kubelka-Munk theory [18] and the pKa shift was recorded
(ApKa -- 1.85). To show that the effect was not confined to tetrabutylammonium
bromide the procedure was repeated, using a fresh sample of immobilized indicator,
with cetylpyridinium chloride, and a similar effect was noted (ApKa = 3.37).
It was shown that the effect was not peculiar to cationic surfactants by carrying
out a similar experiment using sodium dodecylbenzene sulphonate (2.8 x 10 -4 M).
A marked pKa shift occurred in the opposite direction to that induced by the
cationic surfactants, a shift so large that it was impossible to fully convert the
indicator to its basic form under these conditions. The pKa was consequently
estimated by extrapolation of the reflectance curve beyond pH 13 (see Table 1).
pH Transition Interval of Bromothymol Blue 289

iiI--25
Fig. 1. Response of immobilized bromothymol blue in the
4 6 ,9 10 12 presence of tetrabutylammonium bromide; O no surfactant,
pH [] 2.8 x 10-4 M surfactant

Table 1

pKa of bromothymol blue


Surfactant
(2.8 x 10 - 4 M) Solution Immobilized

No surfactant 7.24 9.97


Tetrabutylammonium -- 8.12
Cetylpyridinium 5.90 6.60
Tetrahexylammonium -- 6.05
Tetraoctylammonium -- 5.05
Dodecylbenzenesulphonate 7.24 14.0 __+0.3

At the outset it was thought that the pKa shift was a result of coadsorption of
the surfactant on the dyed matrix. This would impart a charge to the matrix surface
which would attract ions of opposite charge from solution, including H + or O H -
ions. This would have the effect of altering the pH of the solution adjacent to the
matrix surface. As the co-adsorbed indicator "sees" only the interfacial solution its
transition interval would be shifted relative to its value in the bulk solution.
However the observed effects did not preclude a dye-surfactant complex, or ion
pair, being formed which might have altered the electronic distribution in the
c h r o m o p h o r e [19], thus affecting the pKa of the dye. To distinguish these possi-
bilities the effect of the presence of cetylpyridinium chloride (5.6 x 10 -4 M) and of
sodium dodecylbenzenesulphonate (5.6 x 10 -4 M) on the pKa of b r o m o t h y m o l
blue in aqueous solution was examined. It was found that whilst the cationic
surfactants shifted the pKa to a lower value (ApKa = 1.34) the anionic surfactant
had no effect, a p h e n o m e n o n first noted by Hartley [20], who reported that the
spectrophotometric pKa of arrange of indicators, including bromothymol blue, was
affected only when the charge on the surfactant was of opposite sign to that on the
dissociated indicator molecule.
The fact that a cationic surfactant associated with b r o m o t h y m o l blue in aqueous
solution whereas the similarly shaped anionic surfactants did not, can be explained
by electrostatic attraction/repulsion of unlike/like charges respectively. The cationic
290 D.C. Ashworth and R. Narayanaswamy

surfactants may well have been attracted to the bromothymol blue anion, forming
an ion pair in which the charge on the SO~- group would be localised, thus permitting
easier access to the chromophore by hydroxyl ions than with the dye anion alone,
hence causing a pKa shift to a lower value. In addition, the localisation of the charge
on the SO~ group would facilitate proton release from the chromophore, inherently
altering the pKa to a lower value and reinforcing the above effect. The anionic
surfactants, on the other hand, may have been repelled by the dye, resulting in no
association, so giving no effect on the pKa of the dye.
The fact that the transition intervals of both dissolved and immobilized bromo-
thymol blue were shifted by cationic surfactants did not distinguish between surface
co-adsorption and dye/surfactant association. However the effects of anionic sur-
factants, which differed between dissolved and immobilized dye, showed that dye/
surfactant association could not be the mechanism giving rise to a pKa shift of
the adsorbed dye, and the most probable mechanism was that of surface co-
adsorption.
According to the above theory non-ionic surfactants should have had no effect.
To test this, the pKa of the immobilized dye was determined in the absence and
presence of Triton X 100 (0.002~o m/v). As expected no pKa shift was observed at
this concentration. However, on increasing the concentration to 0.02~ m/v the dye
exhibited its yellow (uncharged) colour even at a reservoir pH of 11.8.
This result was initially surprising, and when it was realised that the critical
micelle concentration of Triton X 100 was 0.014~ m/v, the possibility was considered
that micelles in solution were responsible for the colour changes. If so, then micelles
would have had to be adsorbed on XAD 4, whereas individual surfactant molecules
would not, an inherently unlikely situation. It was considered far more likely that
individual molecules would have been adsorbed in preference to micelles, in which
case the difference in behaviour between ionic and non-ionic surfactants may be
explained as follows. The XAD 4 readily adsorbs a monolayer of ionic surfactants.
Once this layer has been adsorbed the charged surface repels any other surfactant
ions in the vicinity, consequently, at least for dilute solutions, the adsorption process
stops at one monolayer. However no such restriction applies to non-ionic sur-
factants. Multilayers can readily be built up and may reach a thickness such that
the co-adsorbed dye is shielded from the aqueous solution. Being in a non-aqueous
environment the dye would revert to its uncharged (yellow) form irrespective of the
pH of the reservoir solution.
The above reasoning suggested that the pKa shift of an adsorbed indicator
should rise as the concentration of co-adsorbed surfactant rises (up to monolayer
coverage). Therefore the pKa shift could be taken as an indirect indication of the
concentration of adsorbed surfactant. The adsorption behaviour of the tetraalkyl-
a m m o n i u m bromides and of cetylpyridinium chloride was examined by determining
the pKa shift as a function of initial concentration of surfactant in solution. The
results (Fig. 2) implied that the concentration of adsorbed surfactants rose steeply
with increasing solution concentration and then tailed off to a plateau as further
adsorption ceased. This presumably occurred at monolayer coverage, although this
was not proved.
It can be seen from Fig. 2 that a surfactant concentration of 2.8 x 10 .4 M gave
an adsorbed concentration well into the plateau region. An indication of the effect
pH Transition Interval of Bromothymol Blue 291

5 o

~pH
Fig. 2. p K a shift of immobilized
bromothymol blue as a function
of surfactant concentration; O
tetrabutylammonium bromide, []
cetylpyridinium chloride, /, tetra-
r ~ ~

1 } 3 ~ s 6 hexylammonium bromide,
Surfactant Concentration (M x 10 x) tetraoctylammonium bromide

6-

5-

,~-
~pH
~J

2-

7-
Fig. 3. Limiting p K a shift of immobi-
s 16 2~ 32 ~U lized bromothymol blue as a function
No of CoFbon Atoms /n Tetraa/kytammon/um Cation of no. of carbon atoms in surfactant

of surfactant shape and size on the plateau pKa shift of a co-adsorbed indicator was
obtained by determining the plateau pKa shift as a function of size of surfactant (at
constant initial solution concentration of 2.8 x 10 -4 M). Fig. 3 and Table 1 present
the results of this study, and several features are shown, which are discussed below.
Firstly the surfactant needs to possess > 14 carbon atoms to be significantly
adsorbed on to XAD 4 from aqueous solution, smaller molecules being too
hydrophilic.
Secondly the plateau pKa shift itself appears to reach a limiting value of ~- 5.5
pH units "-~ 40 carbon atoms. The evidence suggests that the pKa shift is governed
by the packing density of the surfactant molecules on the substrate, which obviously
increases as the solution concentration of surfactant increases. The plateau density
is a compromise between the hydrophilicity of the surfactant, which increases the
packing density as the surfactant size increases, and electrostatic repulsion, which
limits this process. It appears that at approx. 40 carbon atoms the hydrophilicity
has reached a constant value and the packing density thus remains constant.
Thirdly cetylpyridinium chloride is seen to lie on the curve joining the tetraalkyl-
a m m o n i u m series. This indicates that the number of carbon atoms in the surfactant
is the most important factor determining its packing density, with its precise shape
exerting little, if any, influence on the pKa of a co-adsorbed dye.
292 pH Transition Interval of Bromothymol Blue

Conclusions
The present work has shown that the presence in aqueous solution of ionic sur-
factants possessing > 14 carbon atoms altered the spectrophotometric pKa of
bromothymol blue adsorbed on to XAD 4. The effects may be explained in terms
of co-adsorption of the surfactant on the surface of the XAD 4 matrix.

Acknowledgement. The authors wish to thank the Department of Trade and Industry and a consortium
of industrial companies for funding the Optical Sensors Research Unit (OSRU) in which this work
was carried out.

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Received September 5, 1990. Revision February 8, 1991,

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