Colloids and Surfaces A 586 (2020) 124241

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Colloids and Surfaces A

journal homepage: www.elsevier.com/locate/colsurfa

Effects of nonionic surfactant (TX-100) on solubilizing power of cationic T

surfactants (CTAB and CPC) for Direct Red 13
Abdul Rehmana, Muhammad Usmana,*, Tanveer Hussain Bokharia,
Hafiz Muhammad Abd Ur Rahmanb, Asim Manshaa, Muhammad Siddiqc, Aamir Rasheedd,
Mehr Un Nisaa
a
Department of Chemistry, Government College University, Faisalabad, 38000, Pakistan
b
Department of Chemistry, Government College Women University, Sialkot, Pakistan
c
Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan
d
Department of Chemistry, The Islamia University of Bahawalpur, Bahawalpur, 63100, Pakistan

G R A P H I C A L A B S T R A C T

DR-13 is anionic in nature so it favorably tends to reside near to positively charged surface of simple and mixed micelles CTAB and CPC.

A R T I C LE I N FO A B S T R A C T

Keywords: In present study, the solubility of anionic dye, Direct Red 13, has been, spectroscopically and con-
Cationic surfactants ductometrically, investigated in micellar media of cationic surfactants; Cetylpyridinium chloride (CPC),
Anionic dye Cetyltrimethylammonium bromide (CTAB) and mixed micellar media of each with nonionic surfactant, Tritron
Mixed micelles X-100. The spectral behavior of dye in presence of surfactants was regularly monitored from pre- to post-micellar
Solubilization
region of concentration. The UV–vis spectroscopy was applied for estimation of extent of solubilization in terms
Conductometry
Absorption spectroscopy
of partition coefficient (Kx), binding constant (Kb) and Gibbs free energy of corresponding processes. The ad-
dition of nonionic surfactant in ternary solution of dye was made to elucidate the role of mixed micelles on
solubility of dye. The electrical conductivity data, measured at different temperatures, was used for detection of
CMC and calculation of different thermodynamic parameters like; entropy (ΔSm), enthalpy (ΔHm) and Gibbs free
energy change (ΔGm) of micellization of selected surfactants. Results reveal the spontaneity of binding and
partitioning of dye in aqueous and micellar phase for all the used surfactant systems.

⁎
Corresponding author.
E-mail address: musman@gcuf.edu.pk (M. Usman).

https://doi.org/10.1016/j.colsurfa.2019.124241
Received 23 August 2019; Received in revised form 12 November 2019; Accepted 15 November 2019
Available online 16 November 2019
0927-7757/ © 2019 Elsevier B.V. All rights reserved.
A. Rehman, et al.
1. Introduction
The surfactants are organic compounds composed of hydrophobic
tail and hydrophilic head group; the inclusion of two different moieties
within a single unit enables them to exhibit fascinating and exclusive
behavior and makes them fundamental substances of daily usage in
every field of life from domestic to industrial as detergents, solubilizers,
emulsifiers, wetting agent, drug delivery, leveling, oil recovery, corro-
sion inhibitor, flotation and foaming agents [1–3]. The amphiphilic
nature of surfactant molecules in aqueous solution not only renders
them to arrange themselves on water-air interface to minimize the
Gibbs free energy of the system but also favors self-aggregation to form
colloidal size particles, called micelles, when their concentration ex-
ceeds critical micelle concentration, CMC [4]. According to the stability
perspective, after interfacial adsorption, micellization is the only way to
stabilize the system when concentration of surfactant is gradually being
increased. The process of micellization is spontaneously driven by non-
covalent forces i.e. hydrophobic interaction, hydrogen bonding or van
der Waals forces. The hydrophilic exterior and hydrophobic interior of
the micelles give them identity resembling to the bio-membrane,
therefore, micelles are also used in vitro studies, for example, drug-
surfactant interaction [5,6]. The process of detergency and solubiliza-
tion is directly associated with micellization. The solubilization is
spontaneous increase in solubility of water insoluble or sparingly so-
luble compounds by means of micellar media of surfactant to form
thermodynamically stable isotropic solution. In other words it is the
partitioning of water insoluble compounds between micellar and bulk
aqueous phase, through dynamically reversible interaction, governed
by Nernst’s distribution law [7–13]. The process of solubilization is
extensively applied in textile dyeing industries; where surfactant solu-
tion functions as solubilizer to improve dispersion, homogeneity, so-
lubility and stability of dye solution. Moreover, colloidal solution of
surfactant plays two key roles in dyeing bath; first of all it facilitates the
adsorption and fixation of dye on substrate and secondly it simulta-
neously removes loosely bound dye molecules via solubilization. Hence,
application of surfactants in dyeing bath is according to the principles
of Green Chemistry in many aspects; as micellar media not only pro-
hibits the use of hazardous organic solvent but also decreases the
quantity of dye in waste water by disintegrating the dye-aggregates and
improving the efficiency of absorption on substrate [14,15].
Dyes are structurally complex unsaturated organic compounds
which absorb visible light to impart color. The dye molecules are
composed of two important structural parts; chromophore and aux-
ochrome which impart characteristic colors to them. The chromophoric
groups have extensive delocalization of electrons while auxochromic
groups are substituents attached to the chromogen, which have po-
tential to strengthen the intensity of absorption of chromophore [16].
Apart from self-aggregation of surfactants, dye molecules undergo self-
aggregation as well, which leads to change in position and intensity of
spectral band. These aggregations are categorized as J-aggregate and H-
aggregate. The plane-to-plane and end-to-end stacking of dye molecules
construct H-aggregate and J-aggregate, respectively. The tilt angle of
joining molecules is below 32° and approaches to 90° for J- and H-
aggregates, respectively. H-aggregate and J-aggregate are characterized
by blue and red shift, respectively, in absorption maxima of dye. These
dye-aggregates make the dyeing process ineffective and imperfect un-
less the micellar media is applied to break them down. Since the last
few decades many researchers and scientists have been trying to im-
prove dyeing in different ways but still usage of surfactant is matter of
importance [17–19].
The detergents being used in our daily life are the mixtures of ca-
tionic and anionic surfactants along with some additives and said for-
mulated mixtures depict superior properties of detergency and solubi-
lization in comparison to individual components [4]. Most importantly,
performance of the mixed micelles can be easily modified according to
the requirement by altering the ratio participating components [3]. In
2
Colloids and Surfaces A 586 (2020) 124241
this regard, Mandal A. B. and Moulik S. P. have elaborately discussed
the important aspects of the interaction between oppositely charged
surfactants in the light of coacervate formation and solubilization [20].
The mixed micellization shows synergism in physicochemical proper-
ties by assembling thermodynamically stable more hydrophobic mi-
celles which are more suitable for solubilization. Thus, this synergistic
phenomenon can also be greatly favorable for the environment as it
lessens the quantity of surfactants to be released in waste water
[21,22]. In the mixed surfactant systems, for instance, nonionic sur-
factant molecules arrange themselves among the head groups of ionic
surfactant to weaken the strength of repulsive forces and thus promote
the phenomenon micellization to take place at comparatively low CMC
[23]. Alam Md. S. et al. reported that mixed micelle formation of TX-
100 is supported by amphiphilic drug, amitriptyline hydrochloride
[22]. In the mixed surfactant systems, work required in transferring of
surfactant molecules from a monolayer at surface to the micelle for-
mation becomes negligible. Furthermore, the interaction between two
components of the composite micelle is more attractive than the self-
interaction of two individual components before mixing [24]. In fact,
low CMC is the sign of high concentration of micellized surfactants and
such systems are considered potential candidate for enhanced solubi-
lization. Furthermore, high cloud point of mixed micellar media is the
most important one which enables them to apply under wider range of
temperature and salinity than simple micellar system [25–29].
Previously, we have addressed solubilization of many dyes; reactive
black 5 and 8, reactive blue 19, reactive yellow 86, reactive orange 122
and reactive red 223 using different surfactant systems [14,17,30,31].
In present work, we are determined to investigate partitioning of direct
dye viz. DR-13 in different formulations of mixed micellar media of
CTAB/TX-100 and CPC/TX-100 using conductometric and UV–vis
spectroscopic techniques. The effects of cationic/nonionic mixed mi-
cellar media on solubility of dyes have little been investigated in past,
therefore, to explore the mechanism and modify the method of appli-
cation, indeed, innovation in work is needed. We anticipate that present
study will be supportive for selection of best micellar media and op-
timum conditions for spontaneous encapsulation of dye. Structures of
chemicals used in this study are given in Fig. 1.
2. Calculated parameters
2.1. Thermodynamic parameters
In this work, conductivity-concentration plot has been employed for
detection of critical micelle concentration, CMC. The sharp change in
conductivity, with respect to concentration of ionic surfactants in above
plot, gives the indication of CMC. The mathematical Eq. (1) is usually
used for calculation of Gibbs energy change of micellization, ΔGm, of
surfactants [32].
ΔGm = (2 − α )RTlnX cmc (1)
In above expression, α denotes degree of dissociation and it is the
ratio of slopes of post micellar to premicellar regions of surfactant
concentration. Here, T, R and XCMC are absolute temperature, universal
gas constant and CMC in form of mole fraction, respectively.
α = S2/ S1 (2)
Here, S1 and S2 represent the slopes in the pre-micellar and post-mi-
cellar regions of surfactant concentration, respectively. The Eqs. (3) and
(4) were used to calculate enthalpy, ΔHm, and entropy change, ΔSm, of
micellization of surfactants in dye solution, respectively.
∂ (logXcmc) ⎤
ΔHm = −2.303(2 − α )RT 2 ⎡
⎢
⎣ ∂T ⎥
⎦ (3)
ΔHm − ΔGm
ΔSm =
T (4)
A. Rehman, et al. Colloids and Surfaces A 586 (2020) 124241

(CTAB), Cetylpyridinium chloride (CPC) and nonionic surfactant;

Triton X-100 (TX-100) of 99.9 % purity were purchased from Sigma-
Aldrich (USA based, now Merck, Germany) and used as received. While
anionic direct dye i.e. DR-13 (molar mass 712.66 g/mol) of industrial
dyeing grade was provided by Haris dyes and pigments, Faisalabad,
Pakistan.

3.2. Experimental methods

The series of surfactant solutions of CPC and CTAB ranging from

Fig. 1. Structures of chemicals used (a) DR-13 (b) CTAB (c) CPC (d) TX-100.
2.2. Calculation of binding and partition parameters
sub-micellar to post-micellar regions of concentration were prepared in
dye solution of fixed concentration, 1.5 × 10−4M. For mixed micelli-
zation calculated amounts of TX-100 were added in ternary solutions of
CTAB/DR-13 and CPC/DR-13 in water, individually, to prepare dif-
ferent formulations of mixed micellar media. Micellization and solubi-
lization are dynamic processes; therefore, overnight stay time is com-
pulsory to be given to the solutions for establishment of dynamic
equilibrium. Simple and differential absorption spectra were recorded
with the help double beam UV–vis spectrophotometer (Shimadzu UV-
1800). In spectroscopic study, distilled water and dye solution were
placed in reference compartment for simple and differential absorption
measurements, respectively, however surfactant solutions prepared in
presence of DR-13 were placed in sample compartment [1,36]. The
electrical conductivity of solutions of CTAB and CPC in presence of dye
was measured using conductivity meter, Hanna EDGE (HI 2003-02),
with cell constant 0.864 cm-1. The electrode of conductivity meter was
dipped in 0.01 N solution of KCl, prepared in deionized water (6.88μS/
cm), for calibration. The conductivity was recorded at different tem-
pertures from 293 K to 323 K with interval of 10 K and the con-
centration of surfactants was regularly changed from premicellar to
postmicellar region.

In surfactant system the molecules of dye, DR-13, are partitioned

4. Results and discussion
between bulk aqueous and micellar phases. For quantitative measure of
partitioning, in term of partition coefficient, from differential spectro-
4.1. UV–vis spectroscopic study
scopic data Kawamura Eq. (5) was applied [33].
1 1 1 4.1.1. Interaction of DR-13 with CTAB
= +
ΔA K c ΔA∞ (Cd + Csmo) ΔA∞ (5) Fig. 2(a) displays UV–vis absorption spectrum of aqueous solution
of DR-13 in absence and presence of different concentrations (0.7 mM
Here Cd is for molar concentration of dye, DR-13, while Csmo stands for
and 1.0 mM) of surfactant, CTAB. In this spectroscopic investigation
analytical concentration of CPC or CTAB, given as Csmo =Cs-CMCo,
concentration of dye was kept constant (1.5 × 10−4 M) and 510 nm was
where Cs is the total molar concentration of added surfactants and
chosen as absorption maxima. It was observed that absorption spectrum
CMCo is CMC of pure surfactant in water in the absence of dye. The
of dye is sensitive to presence of surfactant in micellar and submicellar
differential absorbance of said dye at experimental and infinite dilute
region. Similar observation for dipeptide in the presence of CTAB was
concentration of surfactants is shown by ΔA and ΔA∞, respectively.
reported by Mandal, A. B. et al. [37]. The appearance of hypsochromic
Whereas, Kc is the partition constant with unit of dm3 mol−1 and Kx is
shift (blue shift) in absorption maxima of dye is ascribed to strong co-
the partition coefficient, a dimensionless quantity, which is the multiple
lumbic and hydrophobic interactions between anionic dye and cationic
of Kc and nw. Since, nw is number of moles of water per liter. The cal-
surfactant. Alternatively, it is also reasonable to say that surfactant
culation of Gibbs energy was made by applying Eq. (6). The Benesi-
induced H-aggregation is responsible for blue shift from 510 nm to 490
Hildebrand Eq. (7) was applied to calculate binding constant [34].
nm. Whereas, appearance of hypochromic shift in absorption intensity
ΔGp = −RTlnKx (6) might be the result of dye-surfactant complex formation, which leads to
H-aggregation of dye molecules, by reducing repulsive forces between
dCd 1 1
= + negatively charged dye species [25,38]. Fig. 2(b) shows increase in
ΔA KbΔεCsmo Δε (7) absorbance with concentration of surfactant due to penetration of dye
Here, d is optical path length (1.0 cm), Δε is differential absorption molecules inside the micelle. During the transfer of dye molecules from
coefficient and Csmo is analytical concentration of surfactant. The aqueous to micellar phase, dye aggregates undergo disintegration and
change in Gibbs energy of binding was estimated by following Eq. (8) monomerized dye molecules are incorporated inside the micelle. In
[26,35]. other words, self-association of dye molecules is hindered by CTAB. The
orientation of dye molecules within micelle causes them to have higher
ΔG b = −RTlnKb (8)
absorbance. Although, shift of absorption to the shorter wavelength is
attributed to solvatochromic effect, increase in polarity of micro-
3. Materials and methods environment near dye’s chromophore results in shift of absorption band
towards shorter wavelength. The dye-surfactant ion pair formation in
3.1. Materials used submicellar region brings about redistribution of energy levels in dye
molecule. In vicinity of cationic surfactant, more polar states, n and π*
The Cationic surfactants; Cetyltrimethylammonium bromide molecular orbitals of dye are stabilized. But stabilization of nonbonding

3
A. Rehman, et al. Colloids and Surfaces A 586 (2020) 124241

Fig. 2. (a) Represents absorbance of DR-13 in presence and absence of CTAB, and (b) Plot of simple absorbance at λmax of DR-13 as a function of CTAB concentration.

Fig. 3. (a) Plot of differential absorbance of DR-13 as a function of CTAB concentration (b) Plot for calculation of binding constant Kb (c) Plot for calculation of
partition constant Kx for the DR-13/CTAB system (d) Plot of differential absorbance of DR-13 in different formulations of CTAB/TX100 mixed micellar systems.

molecular orbitals, n-orbitals, is greater than antibonding molecular
orbitals, π*-orbitals. Consequently, blue shift was observed for n→π*
electronic transitions. When concentration of surfactant exceeds CMC
the dye-surfactant ion pairs undergo rearrangement to assemble mi-
celles with solubilized dye. No change in absorption maxima of solu-
bilized dye confirms the location of chromophore inside the micelle as
same as was in ion-pair [39–42]. In postmicellar region intensity of
absorption seems to be less prominent due to maximum incorporation
of dye molecules into micelles [1]. In order to investigate dye-surfactant
interaction and partitioning of dye between two phases, water and
micellar, differential spectroscopic technique has been applied. The
differential absorbance of dye, in presence of surfactant, is directly
proportional to the concentration of micellized surfactants as depicted
by Fig. 3(a). It is believed that below CMC neither micelles exist nor
solubilized dye so differential absorbance must be zero. The differential
spectroscopic data given in Table 1 was plotted; Fig. 3(b) and 3(c), to

4
A. Rehman, et al. Colloids and Surfaces A 586 (2020) 124241

Table 1
Concentration of CTAB, Cs, differential absorbance, ΔA, critical micelle concentration of pure CTAB, CMCo, concentration of dye, Cd and analytical concentration of
surfactant, Csmo for calculation of binding and partitioning parameters for CTAB/DR-13 systems.
103 Cs 103 Δ A 1/Δ A 104 Cd 103CMCo 103 Csmo (Cd+Csmo) 1/Cd+Csmo
(M) (M) (M) (M) (103 M) (M−1)

6.00 35.0 ± 0.001 28.6 1.5 1.0 5.00 5.15 194.17

5.77 34.0 ± 0.002 29.4 1.5 1.0 4.77 4.92 203.28
5.36 33.0 ± 0.001 30.3 1.5 1.0 4.36 4.51 221.87
5.00 32.0 ± 0.001 31.3 1.5 1.0 4.00 4.15 240.96
4.84 31.0 ± 0.001 32.3 1.5 1.0 3.84 3.99 250.71
4.69 30.0 ± 0.003 33.3 1.5 1.0 3.69 3.84 260.59
4.55 30.0 ± 0.002 33.3 1.5 1.0 3.55 3.70 270.60
4.41 29.0 ± 0.002 34.5 1.5 1.0 3.41 3.56 280.76
4.29 28.0 ± 0.001 35.7 1.5 1.0 3.29 3.44 291.06
4.17 27.0 ± 0.001 37.0 1.5 1.0 3.17 3.32 301.51
4.05 27.0 ± 0.002 37.0 1.5 1.0 3.05 3.20 312.10
3.95 25.0 ± 0.001 40.0 1.5 1.0 2.95 3.10 322.85
3.85 24.0 ± 0.003 41.7 1.5 1.0 2.85 3.00 333.76
3.75 23.0 ± 0.002 43.5 1.5 1.0 2.75 2.90 344.83
3.66 22.0 ± 0.001 45.5 1.5 1.0 2.66 2.81 356.06
3.57 21.0 ± 0.001 47.6 1.5 1.0 2.57 2.72 367.45
3.49 21.0 ± 0.003 47.6 1.5 1.0 2.49 2.64 379.02
3.41 20.0 ± 0.001 50.0 1.5 1.0 2.41 2.56 390.76
3.26 19.0 ± 0.002 52.6 1.5 1.0 2.26 2.41 414.79

Table 2 micelle which makes attraction between micelles and dye less favor-
Binding constant, Kb, Gibbs energy of binding, ΔGb, Partition constant, Kc, able. The more negative values of ΔGx and ΔGb describe that parti-
Partition coefficient, Kx and Gibbs energy of partition, ΔGp for CTAB/DR-13 tioning of dye in mixed micellar media is more synergistic and spon-
systems at different concentrations of Triton X-100. taneous than single surfactant system [43].
TX100 Kb (dm3/mol) Δ Gb (kJ/ Kc (dm3/mol) Kx Δ Gp (kJ/
(mM) mol) mol)
4.1.3. Interaction of DR-13 with CPC
−9.82 −18.79
0 52.82 35.53 1974.17
The series of ternary solutions of dye (1.5 × 10−4 M) having con-
0.08 183505 −30.02 28426.25 1579236.23 −35.36
0.11 947700 −34.10 187130.0 10396111.94 −40.02 centrations of CPC from 0.084 mM to 0.19 mM were prepared at con-
0.17 329011.1 −31.47 96880.0 5382223.00 −38.40 stant dye concentration. Fig. 4(a) displays the surfactant induced re-
0.20 320387.5 −31.41 54466.67 3025926.17 −36.97 markable effects on position and intensity of spectral band of dye. The
observed blue shift of spectral band from 510 nm to 480 nm is the
consequence of dye-surfactant interaction. The hypochromic shift of
calculate values of binding constant (Kb) and partition coefficient (Kx), spectral band may be due to formation of less absorbing dye-surfactant
respectively. Then these values were used for calculation of their re- ion-pairs. The hypochromic shift in spectra band is also observed due to
spective thermodynamic parameters, for example, Gibbs energy of H-type aggregation of dye molecules supported by oppositely charged
binding (ΔGb) and Partition (ΔGp), as tabulated in Table 2. The value of surfactants [25,38]. Fig. 4(b) demonstrates that increase in absorbance
Kb and Kx is measure of strength of dye-surfactant interaction and is the function of surfactant concentration. This increase is pronounced
quantity of compartmentalized dye, respectively. The negative values of in premicellar region and becomes less prominent in post-micellar re-
ΔGb and ΔGp denote the spontaneity of these processes. gion. The saturation of micelles with dye leads to lessening in steepness
of absorption curve in post-micellar region. Furthermore, fluctuation of
4.1.2. Partitioning of DR-13 in mixed micelles of CTAB and TX-100 absorbance in this region may be the product of dye solubilization in
It is observed that micellar media of mixture of surfactants is better newly assembled micelles [30]. The polarity of solubilizate molecule
choice to enhance the solubility of lipophilic compounds, in aqueous determines its locus inside the micelle. There is a potential gradient
medium, in comparison to that of individual surfactant. In this regard from center to interface of the micelle which governs the mobility of
different formulations of mixed micellar media, CTAB/TX-100, have accommodated dye [36,44]. The hosted dye molecules located near the
been tested for the evaluation of effects of mixing on extent of partition. water-micelle interface absorb light efficiently to strengthen the ab-
The partitioning of dye has been analyzed in mixed micelle of CTAB sorption band [45,46]. Furthermore, no change in position of absorp-
having different concentrations of TX-100: 0.08 mM, 0.11 mM, 0.17 tion maxima confirms that vicinity of chromophore of solubilized dye
mM and 0.20 mM. In mixed micelles, presence of non-ionic surfactant molecules is as same as were in dye-surfactant complex [47]. The
molecules between the hydrophilic heads of cationic surfactants electrostatic forces of attraction bring the positively charged surfactant
weakens the strength of repulsive forces which lead to decrease in CMC and negatively charged dye close to each other to form ion-pair.
of CTAB and, thus, increase in degree of solubilization. Furthermore, However, in micellar region these ion-pairs adhere to the micelle’s in-
mixing of non-ionic surfactant not only stabilize the mixed micelle but terface and ultimately are dragged inside.
also provides more hydrophobic core. The plot given in Fig. 3(d) re- For comprehensive analysis of dye’s distribution between micellar
presents differential absorbance of dye in different formulations of and water phase differential spectroscopy was applied. Fig. 5 consists of
mixed micelles. Keeping in view spectroscopic parameters, given in four plots, where 5(a) highlights the relationship between differential
Table 2, it can be interpreted that increasing concentration of TX-100 absorbance of said dye and concentration of CPC in micellar region. The
strengthens the dye-surfactant interaction and also enhances the values of Kb and Kx were calculated by drawing the plots, 5(b) and 5(c),
quantity of solubilized dye inside the micelle. But inverse trend was from the differential spectroscopic data given in Table 3. The partition
observed after certain limit. The weakening of dye-surfactant interac- coefficient is quantitative measure of extent of partition or degree of
tion and lessening of partition coefficient at higher fractions of TX-100 solubilization and it is also meaningful to derive the value of Gibbs free
is accredited to decrease in ionic character of cationic/nonionic mixed energy, ΔGp, to check out the spontaneity of the process. The large

5
A. Rehman, et al. Colloids and Surfaces A 586 (2020) 124241

Fig. 4. (a) Absorption spectra of DR-13 in absence and presence of CPC (b) Plot of simple absorbance of DR-13 as a function of CPC concentration.

numerical values of Kb and Kx, provided in the Table 4, suggest strong
surfactant-dye interaction and greater quantity of solubilized dye, re-
spectively. The negative values of ΔGp and ΔGb are the indicative of
spontaneous nature of the processes under consideration [14].
4.1.4. Partitioning of DR-13 in mixed micelles of CPC and TX-100
The mixing of two different surfactants introduces synergism in
their properties and making them a better choice, in comparison to
individual components, for different applications. We recall, during
composition of mixed micelles penetration of non-ionic surfactant be-
tween the cationic hydrophilic head of the surfactant minimize the

Fig. 5. (a) Plot of differential absorbance of DR-13 as a function of CPC concentration (b) plot for the calculation of binding constant Kb (c) plot for the calculation of
partition constant Kx for CPC/DR-13 system (d) plot of differential absorbance of DR-13 in different formulations of CPC/TX100 mixed micellar systems.

6
A. Rehman, et al. Colloids and Surfaces A 586 (2020) 124241

Table 3
Concentration of CPC, Cs, differential absorbance, ΔA, critical micelle concentration of pure CPC, CMCo, concentration of dye, Cd and analytical concentration of
surfactant, Csmo for calculation of binding and partitioning parameters for CPC/DR-13 systems.
104 Cs (M) 103 Δ A 1/Δ A 104 Cd (M) 104CMCo (M) 104 Csmo (M) (Cd+Csmo) (104 M) 1/Cd+Csmo (M−1)

3.80 435.0 ± 0.003 2.299 1.50 1.20 2.600 4.100 2439.02

3.65 429.0 ± 0.002 2.331 1.50 1.20 2.454 3.954 2529.18
3.52 423.0 ± 0.003 2.364 1.50 1.20 2.319 3.819 2618.82
3.39 420.0 ± 0.001 2.381 1.50 1.20 2.193 3.693 2707.93
3.28 418.0 ± 0.001 2.392 1.50 1.20 2.076 3.576 2796.53
3.17 412.0 ± 0.001 2.427 1.50 1.20 1.967 3.467 2884.62
3.06 409.0 ± 0.002 2.445 1.50 1.20 1.865 3.365 2972.20
2.97 401.0 ± 0.001 2.494 1.50 1.20 1.769 3.269 3059.27
2.88 400.0 ± 0.001 2.500 1.50 1.20 1.679 3.179 3145.85
2.79 394.0 ± 0.003 2.538 1.50 1.20 1.594 3.094 3231.94
2.71 392.0 ± 0.001 2.551 1.50 1.20 1.514 3.014 3317.54
2.64 390.0 ± 0.002 2.564 1.50 1.20 1.439 2.939 3402.65
2.57 376.0 ± 0.001 2.660 1.50 1.20 1.368 2.868 3487.28
2.50 373.0 ± 0.001 2.681 1.50 1.20 1.300 2.800 3571.43
2.44 377.0 ± 0.002 2.653 1.50 1.20 1.236 2.736 3655.11

Table 4
Binding constant, Kb, Gibbs energy of binding, ΔGb, Partition constant, Kc,
Partition coefficient, Kx and Gibbs energy of partition, ΔGp for CPC/DR-13
systems at different concentrations of Triton X-100.
TX100 Kb (dm3/ Δ Gb (kJ/ Kc (dm3/mol) Kx Δ Gp (kJ/
(mM) mol) mol) mol)

0 29563 −25.51 5129.67 284981.50 −31.12

0.11 512360 −32.57 24228.33 1346018.63 −34.97
0.17 1179450 −34.64 48610.0 2700555.77 −36.69
0.20 1157450 −34.59 46866.67 2603703.91 −36.60

repulsive interaction which leads to drop CMC of mixed surfactant

media. In simple words mixing enhances stability and hydrophobicity
of the micelle. The differential absorbance of dye in different compo-
sitions of CPC/TX-100 mixed micelles is plotted in Fig. 5(d) and dif-
ferent thermodynamic parameters computed from spectroscopic data
are displayed in Table 4. Here, large numerical values of Kb and Kx
confirm strong dye-surfactant interaction between oppositely charged
species and appreciable quantity of hosted dye in surfactant aggregates,
respectively [14,17].

4.1.5. Comparison of interaction of DR-13 with CTAB and CPC

The results explain that DR-13 binds more strongly to the simple
and mixed micelles of CPC, with TX-100, than that of CTAB, with TX-
100. In contrast, extent of partition is significantly higher in simple and
mixed micelles of CTAB. The visual display of ion-pair of dye, DR-13,
with CTAB and CPC has been given in the Scheme 1. It’s important to
note that CTAB and CPC have same symmetry and hydrophobic length
but different head groups. CPC binds strongly with dye but inefficient to
drag it inside the micelle probably due to the hindrance caused by
pyridinium head of the CPC, same was reported by Hosseinzadeh [48].
Scheme 1. Binding of DR-13 (a) with CTAB and (b) with CPC.
However, Mandal, A. B. and Nair, B. U. reported that difference in so-
lubilizing capacity of CTAB and CPC, for electrochemical probe, is due
to different nature of molecular dynamics and counter-ion binding [11]. thermodynamic parameters. The sharp change in conductivity-con-
The solubilization doesn’t merely driven by hydrophilic or hydrophobic centration curve is the indication of CMC of ionic surfactant. Here, two
forces but it is the cumulative response of both of these. Since, the best factors are responsible to bring about this abrupt change (1) decrease in
considered composition of mixed micelles with respect to solubilization activity of free ions due to association with micelle and (2) decrease in
is CTAB in presence of 0.11 mM of TX-100. Scheme 2 illustrates the mobility of micellized surfactant molecules. The ionized surfactant
proposed locus of encapsulated dye inside the mixed micelle (a) CTAB/ molecules are in dynamic equilibrium with unionized ones, as given
TX-100 and (b) CPC/TX-100. below;

CTAB⇌CTA+ + B−
4.2. Electrical conductivity
CPC⇌CP+ + C−

For thermodynamic study of surfactant systems, conductometry is In post micellar region, electrical double layer of oppositely charged
one of the reliable and easily available non-destructive techniques ions is developed around the micelle. However, net charge on the in-
mostly used for detection of CMC of ionic surfactants and calculation of terface of micelle of CTAB and CPC is positive due to unequal

7
A. Rehman, et al. Colloids and Surfaces A 586 (2020) 124241

Scheme 2. (a) Partitioning of DR-13 in mixed micelles of CTAB/TX-100 and (b) in mixed micelles of CPC/TX-100.

Fig. 6. (a) Specific conductivity-concentration plot of CTAB in presence of DR-13 at different temperatures and (b) at 303 K.

Fig. 7. (a) Specific conductivity-concentration plot of CPC in presence of DR-13 at different temperatures and (b) at 303 K.

distribution of counter-ions. The strongly and loosely bound layers of
counter-ions around the micelle-water interface are referred to Stern
and diffused layers, respectively. Since, the drop of electric potential is
rapid for Stern and gradual for diffused layer on moving radially out-
ward. The Fig. 6(a) represents concentration-conductivity plot for CTAB
in presence of DR-13 at four different temperatures. On the other hand,
Fig. 6(b) describes method of detection of CMC of CTAB at 303 K. Si-
milar plots are added, regarding DR-13/CPC system, in Fig. 7(a) and
(b). The numerical values of degree of dissociation, ɑ, and CMC of
concerned surfactants measured at various temperatures were em-
ployed for the calculation of mentioned thermodynamic parameters in
Table 5 and Table 6 for DR-13/CTAB and DR-13/CPC systems,

8
A. Rehman, et al. Colloids and Surfaces A 586 (2020) 124241

Table 5
Critical micelle concentrations of CTAB, CMC, Gibbs energy of micellization, ΔGm, enthalpy of micellization, ΔHm, entropy of micellization, ΔSm, degree of dis-
sociation, α, and degree of counter-ion binding, β for CTAB in presence of DR-13.
Temperature CMC Δ Gm Δ Hm Δ Sm(kJ mol− α β
(K) (103 M) (kJ mol−1) (kJ mol−1) 1
)

293 1.20 ± 0.01 −38.29 −1.44 0.126 0.54 0.46

303 1.07 ± 0.02 −40.36 −1.56 0.128 0.52 0.48
313 1.17 ± 0.01 −41.38 −1.66 0.127 0.52 0.48
323 1.24 ± 0.01 −48.72 −2.03 0.145 0.31 0.69

Table 6
Critical micelle concentrations of CPC, CMC, Gibbs energy of micellization, ΔGm, enthalpy of micellization, ΔHm, entropy of micellization, ΔSm, degree of dis-
sociation, α, and degree of counter-ion binding, β for CPC in presence of DR-13.
Temperature (K) CMC (104 M) Δ Gm (kJ mol−1) Δ Hm (kJ mol−1) Δ Sm (kJ mol−1) α β

293 1.03 ± 0.001 −52.39 0.107 0.193 0.37 0.63

303 1.02 ± 0.002 −53.44 0.113 0.177 0.39 0.61
313 1.01 ± 0.003 −54.29 0.118 0.176 0.42 0.58
323 1.03 ± 0.001 −52.71 0.119 0.171 0.51 0.49

Fig. 8. The CMC versus temperature plots (a) for CTAB and (b) for CPC in presence of DR-13.

respectively. The values of CMC of CTAB and CPC in aqueous solution
of dye at 303 K are accordingly; 1.07 mM and 0.102 mM. The close
agreement was found between CMCs of both surfactants measured by
spectroscopically and conductometrically. No effect of solubilized dye
was observed on CMC of CTAB. For CPC, however, decrease in CMC has
been noted owing to stabilization of micelles upon accommodation of
dye molecules which screen repulsive forces to some extent. The trend
of CMC versus temperature for CTAB and CPC in presence of dye is
shown in Figs. 8(a) and 8(b). The effects of temperature on CMC of
surfactants are not easily predictable or interpretable. The variation in
CMC of amphiphiles with respect to temperature generally depends
upon couple of factors; in aqueous medium hydration of hydrophilic
and dehydration of hydrophobic moieties of surfactant favors micelli-
zation and vice versa. In short, dehydration of hydrophobe leads to
decrease in CMC while dehydration of hydrophile of surfactant leads to
increase in CMC of ionic surfactants. The cumulative magnitude of both
factors decides whether CMC of surfactant will rise or fall with eleva-
tion of temperature [2,14,49].
In subsequent study, large negative values of ΔGm suggest sponta-
neous nature of micellization of CTAB and CPC in presence of dye under
consideration. The positive values of ΔSm and negative values of ΔHm
imply that micellization of CTAB is entropy as well as enthalpy driven
spontaneous phenomenon. While positive values of ΔSm and ΔHm infer
that micellization of CPC is only entropy directed spontaneous phe-
nomenon. According to the Hess’ law overall enthalpy (ΔHm) change of
the system is the summation of enthalpy changes of all the steps
involved such as hydrophilic and hydrophobic interactions, hydration
of hydrophile and counter-ions association to the surfactant assemblies
[49]. The surfactant molecules present in monomeric form in bulk of
the water strengthen the hydrogen bonding among water molecules
around the hydrophobic tail of the surfactant. This action of surfactant
regularizes the arrangement of water molecules in vicinity of hydro-
phobic chain and, thus, mobility of hydrophobe is also restricted.
Hence, both of the said factors decrease entropy of the system which
leads to instability. Thus, to get stability surfactant molecules expel
themselves out of aqueous environment into micelles for sake of nor-
malization of hydrogen bonding among water molecules and restora-
tion of degree of freedom of hydrophobe. Thus, both of the mentioned
factors render the phenomenon of micellization entropically favorable
[17,22,31,47,49–51].
5. Conclusion
The solubilization of anionic dye, DR-13, by micellar media of ca-
tionic surfactants (CTAB and CPC) and mixed micellar media of each in
conjunction with nonionic surfactant (TX-100) has been spectro-
scopically and conductometrically investigated. The conductometric
analysis suggests spontaneous nature of micellization of both reported
surfactant systems. The spectroscopy revealed strong dye-surfactant
interaction, and spontaneous nature of binding and partitioning of the
dye. Although cationic-nonionic mixed micelles being more stable and
more hydrophobic are potential candidates for solubilization but their

9
A. Rehman, et al.
solubilizing power, for anionic dye, decreases with concentration of
nonionic surfactant beyond certain limit due to the decrease in ionic
character of the mixed micelle. It is, therefore, recommended that for
substantial solubilization of ionic solubilizate, the most suitable media
is micellar solution of oppositely charged ionic surfactant with small
fraction of non-ionic surfactant. The experimental results obtained in
this study may be useful for the selection of mixed micellar systems and
optimized conditions.
Contribution of authors
All authors have contributed equally at various stages of planning,
execution and write-up of this manuscript.
Declaration of Competing Interest
There is no conflict of interest among authors to report this work.
Acknowledgments
This manuscript is a part of M. Phil thesis of Mr. Abdul Rehman. We
are thankful to the Department of Chemistry, Govt. College University,
Faisalabad and Department of Chemistry, Forman Christian College (A
Chartered University) Lahore, for technical support.
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