J Surfact Deterg

DOI 10.1007/s11743-016-1810-2

ORIGINAL ARTICLE

Synthesis and Physico-Chemical Properties of Sodium

3-Oxo-2-(3-(4-sulphonatophenyl)triaz-2-enyl)octadecanoate
Anionic Surfactant
El-Sayed A. El-Sharkawy1 • Attia I. Mead2 • Mohamed A. M. Abdel Reheim2 •

Ahmed M. Tolba2

Received: 25 November 2015 / Accepted: 11 March 2016

Ó AOCS 2016

Abstract The novel anionic surfactant sodium 3-oxo-2- to as the tail) which is usually a straight or branched
(3-(4-sulphonatophenyl)triaz-2-enyl)octadecanoate (SSTO) long hydrocarbon chain which is attached to a polar
was prepared from renewable raw materials; glycine and hydrophilic group (referred to as the head group) [1].
palmitic acid. Surface and bulk properties of SSTO were Anionic surfactants are an important class of surfac-
investigated by surface tension and electrical conductivity tants since they have a lower cost of manufacture in
techniques at 298, 308, 318 and 328 K. Surface properties comparison with other classes of surfactants, and they
including critical micelle concentration (CMC), maximum are extensively used in industrial applications specially
surface excess concentration (Cmax), minimum area per soaps and detergents [2]. The concentration of surfac-
molecule (Amin), surface tension at CMC (cCMC), effec- tant needed to initiate micelle formation is called the
tiveness of surface tension reduction (PCMC), efficiency of critical micelle concentration (CMC) [3]. The CMC
surface adsorption (pC20), and degree of counterion dis- can be determined by measuring physical properties
sociation (a) were determined. The thermodynamic that depend on the size or number of particles in
parameters of micellization (DG°mic, DH°mic and DS°mic) solution as a function of concentration [4]. Because
and adsorption (DG°ad, DH°ad and DS°ad) were also their surface activity and dual character arise from the
investigated at 298, 308, 318 and 328 K. The effect of 3 presence of both hydrophobic and hydrophilic moi-
wt% n-propanol, n-butanol and n-pentanol on surface ten- eties, surfactants are among the most versatile mate-
sion and conductivity at 298 K was also determined. rials contributing in many chemical applications [5]
such as oil recovery, detergency, corrosion inhibition,
Keywords Anionic surfactant  CMC  Surface tension  agrochemicals, and beneficiation of ores as flotation
Thermodynamics  Micellization  Adsorption agents [6–8].
The use of renewable raw materials for the synthesis of
surfactants has become a priority in many fields because
Introduction they have been found to have better surface and biolog-
ical properties compared to conventional surfactants and
Surfactants are organic compounds that have the ability considered as one of the preferred choices for food,
to decrease the surface tension of water consisting of pharmaceutical and cosmetic applications due to their low
two moieties: a non-polar hydrophobic group (referred toxicity and rapid biodegradation [9]. Several new sur-
factants have been developed possessing renewable
structural parts like fatty acids [10] and amino acids [11].
& Ahmed M. Tolba This study aimed to prepare a new double-headed anionic
a_tolba23@yahoo.com
surfactant and, furthermore, to investigate the behavior
1
Department of Chemistry, Faculty of Science, and stability of the micellization process for that surfac-
Suez University, Suez, Egypt tant under the effect of either temperature or alcohol co-
2
Department of Chemistry, Faculty of Science, solvent concentration.
Suez Canal University, Arish, Egypt

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Experimental CH3(CH2)14COOH
SOCl2
CH3(CH2)14COCl + SO2 + HCl

(4) (5)
Materials
(3) CH2Cl2 / pyridine
Palmitic acid, glycine, thionyl chloride, sulphanilic acid
and anhydrous sodium sulphate were purchased from
Sigma-Aldrich. All the chemicals, solvents and reagents HO3S N N NH
were of the highest commercial purity and were used COOCH2CH3
without further purification. O
(CH2)14CH3
(6)
Synthesis
Scheme 2 Reaction of triazene derivative (3) with palmitoyl chloride
The synthesis of the anionic surfactant is presented in
Schemes 1, 2 and 3. In Scheme 1, the sulphanilic acid
(60 mmol) was treated with (3.18 g) of anhydrous Na2- filtration and crystallized from n-hexane to give 4-(3-(1-
CO3 dissolved in 10 mL of distilled water with stirring ethoxy-1,3-dioxooctadecan-2-yl)triaz-1-enyl) benzenesul-
for 15 min at 40 °C. The solution was then cooled to phonic acid (6).
0 °C and treated with 2.0 g of NaNO2 dissolved in a In Scheme 3, the anionic surfactant sodium 3-oxo-2-(3-
minimum volume of water. The solution was cooled in (4-sulphonatophenyl)triaz-2-enyl) octadecanoate (SSTO)
ice water and a mechanical stirrer was used with a slow (7) was prepared by the reaction of the equivalent volume
addition of (200 mmol) of HCl. A solution of glycine of 1 M aqueous NaOH (20 mmol) with a stirred solution of
ethyl ester hydrochloride in water was added slowly to compound (6) (10 mmol) in methanol (10 mL) and the
the diazonium salt solution with stirring for 1 h at 0 °C. reaction was allowed to proceed for 3 h. Then, a white
The clear solution was treated with a large excess of solid was extensively precipitated and was collected by
NaOH (40 mL, 10 %) and the triazene precipitated suction filtration, after which was rinsed with ice cold
slowly. Precipitation was normally evident after 30 min, water.
and was completed within 3 h after warming slowly to The IR spectra (KBr) were recorded on a FTIR 5300
room temperature. The resulting reaction product was spectrometer (t, cm-1), the 1H-NMR spectra were recorded
filtered off, washed with water and crystallized from in DMSO-d6 and CDCl3 at 200 MHz on a Varian Gemini
ethanol to give 4-(3-(2-ethoxy-2-oxoethyl)triaz-1-enyl) NMR, the mass spectra were recorded using a 1000 EX
benzenesulphonic acid (3). mass spectrometer at 70 eV and the elemental analysis was
In Scheme 2, palmitoyl chloride was prepared by gently obtained using an Elemental Analyzer Model Varioele-
refluxing a mixture of palmitic acid (26.6 g, 100 mol) and menrar. All the measurements were carried out at the
thionyl chloride (23.7 mL, 200 mol) on a water bath Micro Analytical Center, Cairo University, Egypt.
maintained at 35–40 °C with shaking for 6 h. The excess of
thionyl chloride was removed by washing successively Surface Tension Measurements
with water and the residue was dried over anhydrous
Na2SO4 to collect the liquid palmitoyl chloride. Then, a The surface tension was measured using the maximum
mixture of compound (3) (10 mmol), and palmitoyl chlo- bubble pressure method [12]. The measurement principle is
ride (5) (10 mmol) in CH2Cl2 (30 mL) and pyridine based on applying pressure equivalent to the pressure
(5 mL) was heated under reflux for 8 h. The reaction inside the capillary to return the liquid level in the capillary
mixture was allowed to cool, poured into crushed ice and to the same level as that of the surfactant solution. The
acidified with HCl. The solid product was collected by surface tension (c) was determined from the equation [13]

Scheme 1 Reaction of - +
diazonium salt with glycine NaNO 2 / HCl + - ClNH3 CH2 COOEt
ethyl ester hydrochloride HO 3S NH2 HO3S N 2Cl
Sod.acetate / H 2O

(1) (2)

HO3S N N NHCH2COOCH2CH3

(3)

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Scheme 3 Preparation of
SSTO (saponification process) HO 3S N N NH NaOH NaO3S N N NH
COOCH2CH3 COONa
O CH3OH / H2O O
(CH2)14CH3 (CH2)14CH3
(6) (7)

rg O), 5.23 (br s, 2H, CH2-N), 7.94–8.27 (m, 5H, Ar–H and
c¼ ðhv dv  hdÞ ð1Þ
2 SO3H), 10.40–10.50 (br s,1H, NH). The mass spectrum
where r is the radius of the capillary tube, g is the gravi- showed a very intense molecular ion peak at 287 and a
tational acceleration, hv is the difference in water levels in number of fragments agreed with the proposed structure.
manometer created by the pressure, h is the depth of the The foregoing results prompted us to investigate the
capillary below the solution level, dv is the density of water synthetic potentiality of stable triazene (3) toward palmi-
and d is the density of surfactant solution. toyl chloride. Thus, treatment of triazene derivative (3)
with palmitoyl chloride (5) in refluxing methylene chlo-
Electrical Conductivity Measurements ride containing a catalytic amount of pyridine (Scheme 2)
afforded 4-(3-(1-ethoxy-1,3-dioxooctadecan-2-yl)triaz-1-
The electrical conductivity of surfactant solutions was enyl)benzenesulphonic acid (6) [18]. The structure of
determined with a digital conductivity meter (Pasco compound (6) was established as a sole reaction product
Xplorer GLX, USA) using PS-2116 conductivity sensor based on its spectral data. Compound (6) formed pale
having the range of 0–10000 lS/cm with accuracy yellow crystals after recrystallization from n-hexane with
of ±10 % and resolution of 0.1 % or better. The instru- yield (69 %) and mp 50–52 °C. The IR and 1H-NMR
ment was calibrated using the conductivity calibration spectra of compound (6) revealed the following bands and
standard solution. signals; IR (KBr) m (cm-1) = 3200 (NH), 2917–2849
The measurements of surface tension and electrical (CH-aliph), 1702 (C=O); 1H-NMR (CDCl3) d
conductivity were performed at 298, 308, 318 and 328 K in (ppm) = 0.89 (t, 3H, CH3, J = 8 HZ), 1.27–1.32 (m, 24H,
a thermostatic water bath having a temperature control 12CH2), 1.33 (t, 3H, CH3, J = 4 HZ), 1.61 (s, 1H, CH),
accuracy of ±0.01 K. 1.64 (t, 2H, b-CH2, J = 8 HZ), 2.36 (t, 2H, a-CH2, J = 8
HZ), 4.30 (q, 2H, CH2), 7.28–8.39 (m, 6H, Ar–H ? SO3H
and NH). The mass spectrum of compound (6) revealed
Results and Discussion the molecular ion peak at m/z = 525 (M?) corresponding
to C26H43N3O6S.
Characterization of the Prepared Compounds Then, compound (6) was then submitted to saponifica-
tion at room temperature with an aqueous methanolic
The reaction of diazonium salts with proteins has been solution of NaOH, from which the target SSTO (7) was
extensively used as a structural probe, typically in the easily isolated (Scheme 3). The structure of compound (7)
elucidation of the topography of the active sites of enzymes was established as a sole reaction product based on its 1H-
[14]. The azo-proteins formed in this way arise largely NMR spectrum. Compound (7) was formed as white
from diazo-coupling with the activated aromatic rings of crystals from DMSO with a yield of 62 % and a mp
tyrosine and histidine residues and the e-amino group of 280–282 °C. The 1H-NMR spectrum of compound (7)
lysines [15]. Thus, the reaction of aryldiazonium salt (2) revealed the following signals; 1H-NMR (DMSO-d6) d
with glycine ethyl ester in aqueous solution containing (ppm) = 0.85 (t, 3H, CH3, J = 4 HZ), 1.24–1.32 (m, 24H,
sodium acetate produced the stable triazene derivative (3) 12CH2), 1.48 (t, 2H, b-CH2, J = 8 HZ), 1.91 (s, 1H, CH),
(Scheme 1) where the diazonium ion attacked at the NH2 2.18 (t, 2H, a-CH2, J = 8 HZ), 6.96–7.75 (m, 4H, Ar–H),
moiety and showed no tendency to attack at the activated 8.15 (s, 1H, NH).
CH2, which would give rise to hydrazone formation [16,
17], based on the spectral data. Compound (3) formed Critical Micelle Concentration (CMC)
brown crystals after recrystallization from ethanol with
yield (83 %) and mp 210–212 °C. The IR and 1H-NMR The CMC data obtained from surface tension and electrical
spectra of compound (3) revealed the following bands and conductivity for SSTO at various temperatures are listed in
signals; IR (KBr) m (cm-1) = 3434 (NH), 3100 (CH- Table 1. Figure 1a shows the CMC obtained from surface
arom), 2950–2850 (CH-aliph), 1650 (C=O); 1H-NMR tension as a function of temperature. SSTO was found to
(DMSO-d6) d (ppm) = 1.20 (t, 3H, CH3), 4.18 (q, 2H,CH2- have lower CMC value (136 lM) than SDS (8200 lM) at

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Table 1 CMC values of SSTO from different methods in aqueous Table 2 CMC values of SSTO from different methods in 3 wt% n-
solution at various temperatures alcohol solution at 298 K
T (K) CMCa (lM) CMCb (lM) Type of alcohol CMCa (lM) CMCb (lM)

298 136 ± 0.01 139 ± 0.01 – 136 ± 0.01 139 ± 0.01

308 168 ± 0.02 170 ± 0.01 n-Propanol 109 ± 0.01 125 ± 0.05
318 204 ± 0.04 220 ± 0.01 n-Butanol 95.50 ± 0.01 105 ± 0.02
328 237 ± 0.01 239 ± 0.02 n-Pentanol 83.20 ± 0.01 86.20 ± 0.01
a a
Determined from surface tension Determined from surface tension
b b
Determined from electrical conductivity Determined from electrical conductivity

298 K [4]. This suggests that SSTO more readily forms micellization [3]. The decrease in CMC had become more
micelles due to the increased length of the hydrophobic tail pronounced with the increase in the alcohol alkyl chain in
and modified head group structure. It was evident from solutions containing an identical alcohol concentration
Fig. 1a that the CMC increases with increasing tempera- (Fig. 1b).
ture. The effect of temperature on the CMC of an ionic
surfactant in aqueous solution is usually analyzed in terms Surface Tension
of two opposing factors. The increase in temperature
reduces the hydration of the hydrophilic groups which Representative plots of c versus the log concentration of
favors micellization. On the other hand, the increase in SSTO are shown at various temperatures in Fig. 2a and
temperature also disrupts the structured water surrounding with the effect of added alcohol in Fig. 2b. A linear
the hydrophobic group which disfavors micellization [19]. decrease in c was observed with the increase in surfactant
Figure 1a suggests that the second effect is predominant in concentrations up to the CMC because the amphiphilic
the temperature range studied. structure caused the surfactant molecules to adsorb at the
Table 2 shows the changes in the CMC with the addition surface [21]. Also, increasing the concentration resulted in
of 3 wt% of n-propanol, n-butanol and n-pentanol at 298 K. an increase in the content of hydrophobic chains in water,
The CMC decreased when various n-alcohols were present leading to a rise in free energy of the system. Therefore, the
in solution compared to aqueous solution. This may be migration of monomers from the bulk to the air/solution
attributed to the incorporation of alcohol molecules within interface increased to minimize that free energy and hence,
the micelle thus increasing the length between polar heads the surface tension is reduced [22]. In all cases, SSTO had
that causing the repulsive interactions to decrease [20]. the ability to decrease c until a constant value (cCMC) which
Also, the hydrophobic part of alcohols may enhance the is defined as the surface tension of the solution at the CMC.
hydrophobic character of the surfactant that mainly favors cCMC was read off directly from Fig. 2 and the data were

Fig. 1 CMC of SSTO obtained from surface tension versus: a absolute temperature in aqueous solution and b carbon number of alcohol at
298 K

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Fig. 2 Surface tension versus log molar concentration of SSTO: a at different temperatures in aqueous solution and b in 3 wt% n-alcohol
solution at 298 K

Table 3 Surface properties of

T (K) cCMC (mN/m) PCMC (mN/m) Cmax 9 106 (mol/m2) Amin (nm2) C20 (lM) pC20
SSTO in aqueous solution at
various temperatures 298 40.75 31.24 2.33 0.71 75.86 4.11
308 38.79 31.62 1.60 1.04 72.61 4.14
318 37.12 31.66 1.46 1.13 73.87 4.13
328 35.33 31.77 1.20 1.38 69.29 4.16

Table 4 Surface properties of SSTO in 3 wt% n-alcohol solution at 298 K

Type of alcohol cCMC (mN/m) PCMC (mN/m) Cmax 9 106 (mol/m2) Amin (nm2) C20 (lM) pC20

– 40.75 31.24 2.33 0.71 75.86 4.11

n-Propanol 37.80 21.90 4.20 0.40 96.16 4.02
n-Butanol 31.60 17.62 3.55 0.47 402.75 3.40
n-Pentanol 26.53 14.64 3.05 0.54 7498.90 2.13

listed in Tables 3 and 4 at various temperatures and for absolute temperature, n is the number of ionic species
various alcohol solutions respectively. It was clear that whose concentration changes with the surfactant concen-
cCMC values decreased with increasing either temperature tration at the interface and is taken as three for SSTO since
or carbon number of n-alcohol. it is a divalent surfactant [24] and NA is Avogadro’s
Based on the results of surface tension, The maximum number. As shown in Table 3, Cmax decreases with
surface excess concentration (Cmax) and the minimum area increasing temperature due to high thermal agitation of
occupied per molecule at the surface (Amin) of SSTO were molecules [25] whereas the Amin values increased upon
calculated using the Gibbs adsorption isotherm equations increasing temperature due to the increase in thermal
[6, 23] motion of monomers at the surface [26]. The greatest value
  of Cmax and the smallest value of Amin at 298 K meant a
1 dc denser arrangement of surfactant molecules at the surface
Cmax ¼ ð2Þ
2:303nRT d log C at that temperature. Table 4 also showed a decrease in Cmax
and an increase in Amin as the alkyl chain of the alcohol
1018
Amin ¼ ð3Þ increased.
Cmax NA
Effectiveness of surface tension reduction (PCMC) can
where dc/d logC is the slope of the surface tension iso- be calculated from the experimental CMC data through the
therms below the CMC, R is the gas constant, T is the relation [7]

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PCMC ¼ co  cCMC ð4Þ The degree of counterion dissociation (a) is calculated

from Frahm’s method [28]
where co is the surface tension of pure solvent and cCMC is
S2
the surface tension of the solution at the CMC. As shown in a¼ ð6Þ
Table 3, PCMC values of SSTO were found to be relatively S1
constant with maximum effectiveness at 328 K with a where S2 is the slope above the CMC and S1 is the slope
reduction of 31.77 mN/m. Also, Table 4 revealed a below the CMC. The calculated values of a for SSTO at the
decrease in the values of PCMC in 3 wt% n-alcohol solu- studied temperature range are given in Table 5 and pre-
tions in comparison with those of aqueous solution. Also, sented in Fig. 4a. The degree of counterion dissociation
efficiency of surface adsorption (pC20) was determined (sometimes called the degree of micelle ionization) for
from the concentration capable of suppressing the surface SSTO was found equal to 0.51 at 298 K while Bales [29]
tension of the solvent by 20 mN/m, C20 [27]. gave a value of 0.27 at 298 K for SDS. This result indicates
pC20 ¼  log C20 ð5Þ a higher ionization of the micelle, thus a weaker binding of
the sodium counterions, compared to SDS, since insertion
The values of pC20 of the prepared surfactant are shown in of a hydrophilic part worked to improve hydration of the
Tables 3 and 4. pC20 increases with increasing temperature surfactant head group and to facilitate ionization [30]. This
suggesting that the hydrophobic tails of SSTO monomers at trend was more pronounced at higher temperatures which
328 K can cover the surface more efficiently than the same is probably due to a decrease in the charge density at the
molecules at lower temperatures. Also, these results showed micelle surface caused by the decrease in the aggregation
a decrease in pC20 with the increase in alcohol carbon number of the micelle [31]. Also, the longer alkyl chain of
number. These results illustrate well the complexity of the SSTO with 16 carbon atoms increased the value of a over
effect of alcohols on surface and micellar properties. that for SDS (12 carbon atoms). Table 6 and Fig. 4b shows
that the increase in the length of the alkyl chain of n-
Electrical Conductivity alcohol caused a decrease in a which had been explained in
terms of both a decrease in surface area per head group at
Figure 3a shows the electrical conductivity (j) versus the micelle surface and an increase in surface charge
surfactant concentration in aqueous solution at various density which resulted in a decrease of ionization [32].
temperatures. As SSTO concentration increased, a contin-
uous increase in the value of j was observed in both the Thermodynamic Parameters of Micellization
pre-micellar and the post-micellar regions. This behavior is and Adsorption
typical for ionic surfactants. The conductivity curves when
various alcohols are added (Fig. 3b) shows the same The standard free energy change (DG°mic), the standard
behavior with no distinguishable changes observed com- enthalpy change (DH°mic) and the standard entropy change
pared the absence of alcohols.

Fig. 3 Electrical conductivity versus molar concentration of SSTO: a at different temperatures in aqueous solution and b in 3 wt% n-alcohol
solution at 298 K

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Table 5 Thermodynamic parameters and degree of counterion dissociation of SSTO in aqueous solution at various temperatures
T (K) DG°mic DH°mic DS°mic DG°ad DH°ad DS°ad a
(kJ mol-1) (kJ mol-1) (kJ mol-1 K-1) (kJ mol-1) (kJ mol-1) (kJ mol-1 K-1)

298 -32.87 -20.47 0.042 -46.26 -33.86 0.042 0.51

308 -32.50 -21.42 0.036 -52.30 -41.23 0.036 0.54
318 -31.90 -22.21 0.031 -53.54 -43.85 0.031 0.58
328 -31.64 -23.13 0.026 -58.05 -49.53 0.026 0.61

Fig. 4 Degree of counterion dissociation of SSTO versus: a absolute temperature in aqueous solution and b carbon number of alcohol at 298 K

Table 6 Standard free energy change of micellization and adsorption thermodynamically stable as shown in Table 5. It is clear
and degree of counterion dissociation of SSTO in 3 wt% n-alcohol that DG°mic became less negative with increasing temper-
solution at 298 K
ature indicating that the rise in temperature disfavored
Type of alcohol DG°mic (kJ mol-1) DG°ad (kJ mol-1) a micellization which is in agreement with the CMC results.
Micellization is an exothermic process (since DH°mic is
– -32.87 -46.26 0.51
negative) with attractive London-dispersion interactions
n-Propanol -26.675 -31.892 0.82
playing a major role in micelle formation [33]. This
n-Butanol -27.979 -32.936 0.78
exothermic behavior may be explained as a result of the
n-Pentanol -29.326 -34.122 0.74
decrease in energy required to break up the iceberg water
structure around the hydrophobic chains [20]. DH°mic was
dependent on temperature and became more negative at
(DS°mic) of micellization for SSTO were calculated from
higher temperatures.
Eqs. 7–9 [7, 20].
The large negative DG°mic contributed to the change in
DGomic ¼ ð2  aÞRTLnCMC ð7Þ entropy of the system. There are two basic opposing struc-
dðDGomicc =TÞ tural processes which occur during micellization [34]:
o
DHmic ¼ ð8Þ (I) destruction of the iceberg like structured water molecules,
dð1=TÞ
known as ‘‘flickering clusters’’, surrounding the hydrocarbon
o
DHmic  DGomic chain that leads to a positive entropy change, and (II) rear-
DSomic ¼ ð9Þ
T rangement of randomly oriented monomers into micelles
The plots of DG°mic, DH°mic and DS°mic as a function of that leads to a negative entropy change. The data in Table 5
temperature are shown in Fig. 5a. The DG°mic values are shows that the DS°mic values are all positive indicating that
all negative indicating that the micellization process is micelle formation is favored by entropy gain [31]. It was
spontaneous and that the micelles formed are obvious that process (I) dominates over process (II).

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Fig. 5 Thermodynamic parameters of SSTO of: a micellization versus absolute temperature in aqueous solution, b adsorption versus absolute
temperature in aqueous solution and c micellization and adsorption versus carbon number of alcohol at 298 K in 3 wt% n-alcohol solution

Micellization and adsorption processes of surfactants were found to be linear functions of temperature as shown
occur instantly, but commonly one process may dominate in Fig. 5b. The DG°ad values were negative at all tem-
over the other. This dominance of these two processes is peratures illustrating that SSTO had a great potential to
governed by the thermodynamic variables. The standard adsorb at the surface. DG°ad values are more negative
free energy change (DG°ad), the standard enthalpy change than the corresponding DG°mic values which suggests that
(DH°ad) and the standard entropy change (DS°ad) of the surfactant preferred adsorption at the surface over
adsorption for SSTO were calculated through the Eqs. 10– micellization in the bulk. Exothermic DH°ad and positive
12 [35, 36]. DS°ad values suggest that the adsorption at the air/liquid
interface is favored by heat loss as well as the entropy
PCMC effect [27].
DGoad ¼ DGomic  ð10Þ
Cmax The effect of n-alcohols on DG°mic and DG°ad was also
o dðDGoad =TÞ investigated at 298 K and the results summarized in
DHad ¼ ð11Þ Table 6. The free energy changes were negative in all cases
dð1=TÞ
o
and this negativity increased with increasing hydrophobic
DHad  DGoad
DSoad ¼ ð12Þ chain length of the alcohol. This result is shown graphi-
T cally in Fig. 5c. The contributions of the enthalpy and
The calculated values of DG°ad, DH°ad and DS°ad are entropy terms to both micellization and adsorption creates
reported in Table 5. All the thermodynamic variables a so-called ‘‘compensation phenomenon’’ [37]. Any change

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