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Synthesis and Surface Active Properties of Ethoxyalted

4,5-Dihydroimidazoline Surfactants
a a b a
A. M. Al-Sabagh , R. A. El-Ghazawy , H. M. Abdel Bary & M. Abd Raouf
a
Egyptian Petroleum Research Institute , Cairo, Egypt
b
Chemistry Department , Faculty of Science, Al Azhar University , Cairo, Egypt
Published online: 09 Dec 2009.

To cite this article: A. M. Al-Sabagh , R. A. El-Ghazawy , H. M. Abdel Bary & M. Abd Raouf (2009) Synthesis and Surface Active
Properties of Ethoxyalted 4,5-Dihydroimidazoline Surfactants, Journal of Dispersion Science and Technology, 31:1, 75-83, DOI:
10.1080/01932690903107232

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 Journal of Dispersion Science and Technology, 31:75–83, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932690903107232

Synthesis and Surface Active Properties of Ethoxyalted

4,5-Dihydroimidazoline Surfactants
A. M. Al-Sabagh,1 R. A. El-Ghazawy,1 H. M. Abdel Bary and
M. Abd Raouf1
1
Egyptian Petroleum Research Institute, Cairo, Egypt
2
Chemistry Department, Faculty of Science, Al Azhar University, Cairo, Egypt

Pure oleic acid and four hydrolyzed products of locally fatty oils (namely, coconut, soybean,
linseed, and castor oils) were monoesterified individually with two different polyalkylene poly-
amines. The produced monoesters were used as precursors for imidazoline derivatives. These
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oil soluble imidazolines were ethoxylated by ethylene oxide gas with different ethylene oxide
contents (5, 10, and 20) to prepare water soluble stable imidazoline ethoxylates. The chemical
structure of the synthesized imidazoline ethoxylates were justified through spectroscopy and
surface active properties of the compounds were investigated. The obtained data were discussed
on the basis of variation chemical structure.
Keywords 4.5-dihydroimidazoline, ethoxylated imidazoline, hydrolyzed fatty acid, imidazo-
line surfactants, surfactants

INTRODUCTION emulsifiers (surfactants), viscosity modifiers, and suspend-

Imidazoline was first synthesized in 1858[1] from ammo-
nia and glyoxal whereas more recent syntheses have been
developed from para aldehyde or 2-bromoethyl-1,3-
dioxalane, which, on heating with formamide and
ammonia, yields imidazoline. Desulphurization of thione
intermediate with nitric acid yields imidazoline. Imidazo-
line has a pKa of 7.2 and a pKb of 14.5, and can function
as both weak acid and weak base. Imidazoline forms many
stable salts and is thought to have intermediate properties
between pyrrole and pyridine. Also, imidazoline forms
strong intermolecular hydrogen bonds and associates of
20 to 50 molecules in benzene solution can be formed
giving linear hydrogen-bonded chains.[2] The applications
of imidazoline derivatives are widely used in personal care
industry, antifungal formulations, and in petroleum indus-
try as corrosion inhibitors.
The imidazoline tends to be unstable and care has to be
exercised during manufacture and storage to minimize
color degradation and hydrolysis. For this reason, imida-
zoline is frequently derivitized by quaternization or carbox-
ymethylation.[3] Imidazoline provides excellent corrosion
inhibition and is widely used in the petroleum industry
for corrosion protection in production and refining appli-
cations.[4–7] Other oilfield applications include its use as
Received 6 August 2008; accepted 15 September 2008.
Address correspondence to A. M. Al-Sabagh, Egyptian
Petroleum Research Institute, 1 Ahmed El-Zomor St., Nasr City,
11727, Cairo, Egypt. E-mail: alsabaghh@gmail.com
ing agents. The term ‘‘imidazolines’’ for these applications
is used to describe products that contain mixture of ami-
doamine and imidazoline.[8] Quaternized imidazolines with
an amido moiety are suitable formulations for general oil
and gas field applications.
The main object of this work is to synthesize water soluble
ethoxylated 4,5-dihydroimidazoline surfactans. These
products were synthesized by reacting the hydrolyzed pro-
ducts of some fatty oils with diethylene triamine (DETA)
or triethylene tetramine (TETA) to prepare the monoamide
form. The monoamide were cyclized to obtain the corre-
sponding 4,5-dihydroimidazoline derivatives. The imidazo-
line products were ethoxylated using ethylene oxide gas to
get stable ethoxylated derivatives (surfactants). Our attention
was extended to investigate their surface active properties.
EXPERIMENTAL
Hydrolysis of Fatty Oils
Four different fatty oils (namely, coconut, soybean,
linseed, and castor oils) were separately hydrolyzed to obtain
fatty acid mixture from each. Into a (500-ml) two neck
round bottom flask attached to a reflux condenser and a
mechanical stirrer, add 10 g of fatty oil, 5 g of KOH, and
40 ml of ethanol. The reaction mixture was refluxed until
no oil globules were observed. The reaction mixture was
distilled to recover the alcohol. The residue was dissolved
in (150 ml) hot water and stirred for (90 minutes) until the
mixture became almost clear. A diluted solution of sulfuric

75
 76 A. M. AL-SABAGH ET AL.
TABLE 1
Percentage of fatty acids in hydrolyzed fatty oils[2]
Fatty acids %
Oil Saturated Oleic Linoleic Linolenic Ricinoleic
Coconut 91 7 2 — —
Soybean 15 25 51 9 —
Linseed 10 22 16 52 — Prepared Surfactant
Castor Oil 3 7 3 — 87
acid (300 ml, 98% concentrated in 700 ml water) was
added with continuous stirring for (5 minutes). The oily
layer was separated and filtrated in steam-jacketed funnel
and finally allowed to cool until solidify. The hydrolyzed
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products of fatty oils contained mixtures of fatty acids[9]
(Table 1).
Synthesis of the 4,5-Dihydro Imidazoline Derivatives
In this step, two series of 4,5-dihydro imidazoline surfac-
tants were prepared. Each hydrolyzed fatty oil and oleic
acid was separately condensed with either DETA or
TETA. The first series (series I) was based on DETA,
and the second one (series II) was based on TETA. First,
the reaction was carried out at 140
C for 1 hour using a
Dean and Stark trap to produce the corresponding amides
(see Scheme 1). Then, continuous heating in the range of
180 to 200
C for 3.5 hours led to cyclization of each amide
to the corresponding 4,5-dihydro imidazolines. This is
represented by the second step in Scheme 1.[10]
Synthesis of the Ethoxylated Amino Alkyl Imidazolines
A high pressure stainless steel autoclave (Parr model
4530, USA) of 1-L capacity, 400 psi maximum pressure
and 450
C maximum temperatures was utilized through
ethoxylation reactions. The autoclave was equipped with
a magnetic drive stirrer, an electric heating mantle with
thermocouple inserted in the reactor body, a cooling coil,
a pressure gauge, and a drain valve. Each amino alkyl imi-
dazoline (synthesized in the second step) was charged into
the reaction vessel with triethyl amine as a catalyst
(0.3 wt%)[11] and heated to 80
C with continuous stirring
while passing a stream of nitrogen gas through the system
for 10 minutes to flush out air. The nitrogen stream was
then replaced by ethylene oxide, the first series based on
diethylene triamine was ethoxylated by only one amount
of EO, namely, n ¼ 20. For the second series based on
triethylene tetramine, different EO molar ratios were intro-
duced, namely, n ¼ 5, 10, or 20 EO moles. The difference in
sample weight was used as an indication of the amount of
condensed EO. The ethoxylation was represented by the
third step in Scheme 1.[12–14]
The general chemical structures, IUPAC (International
Union of Pure and Applied Chemistry) name, and abbre-
viation of representative compounds (amide, imidazoline,
and ethoxylate) are shown in Table 2. Fourier transform
infrared spectroscopy (FTIR) was used to confirm their
chemical structures (Figures 1 and 2).
Evaluation of Some Surface Properties of the
Surface Tension Measurements (c)
Different molar concentrations of the synthesized sur-
factants were prepared using double distilled water and
their surface tension were determined at 25
C using
Lecomte De Nouy tentiometer with platinum ring-iridium,
Krüss-K6 (Germany). The instrument was daily regulated
by bi-distilled water (conductivity 1.1  106 ohm1 cm1
at 25
C).[15]
Critical Micelle Concentration
The critical micelle concentration (CMC) of the pre-
pared surfactants was determined by the method adopted
by Larinov et al.[16] The surface tension –ln molar con-
centration isotherms (SVC) were plotted for the prepared
surfactants. The CMC values were determined from the
abrupt change in the slope of SVC curves.[17] The SVC
curves for the ethoxylated samples of Series II surfactants
are represented in Figure 3.
Surface Excess Concentration (CMax)
CMax is a measure of the effectiveness of adsorption of
surfactant at the liquid=air or liquid=liquid interface since
it is the maximum value to which adsorption can be
obtained.[18,19]
CMax can be calculated from Gibbs equation:
Cmax ¼ ð1=RTÞ ðdc=d ln CÞ;
where: CMax is surface excess concentration (mol=cm2), T is
absolute temperature (273 þ
C), R is universal gas
constant (R ¼ 8.314 Jmol1 deg1), and dc=d Ln C is
surface activity (slope of linear portion of SVC curves).
Minimum Surface Area Per Molecule (Amin)
Amin is the minimum area per molecule in nm2=molecule
at the interface.[20] The area occupied by each adsorbed
molecule is given by equation:
Amin ¼ 1016 =ðNA  CMax Þ;
where: NA is Avogadro’s number.
Effectiveness pCMC
The effectiveness of adsorption or surface pressure pCMC
of the surfactants was also calculated using the following
equation.[21]
 ETHOXYALTED 4,5-DIHYDROIMIDAZOLINE SURFACTANTS 77
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SCH. 1. Synthesis of 4,5-dihydro imidazoline derivatives.

pCMC ¼ c0  cCMC ;
where: c0 is the surface tension of water at 25
C; and cCMC
is the surface tension value of the measured solution at
CMC.
RESULTS AND DISCUSSION
Spectroscopic Analysis of the Prepared Surfactants
FTIR of I2, I2Z, and I2ZE20 are illustrated in
Figures 1a–1c, respectively. Figure 1a, for I3, is a typical
amide carbonyl absorption band was observed at
1669.45 cm1 together with a broad band in the range of
3320 to 3559 cm1 region for N-H stretching. The comple-
tion of imidazole derivative formation (I3Z) was confirmed
by the sharp absorption at 1625.7 cm1 (Figure 1b) corre-
sponding to C=N stretching of the imidazoline ring.
However, the characteristic absorption of the iminic
C=N group for imidazoline ring in the usual range
(1603–1635 cm1) rather than in the region of amidic
carbonyl (1640–1670 cm1) confirms the cyclization of the
amides upon continuous heating.[22]
Figure 1c, for I3ZE20, is a sharp band at 1119.84 cm1
for CO stretching vibration of ethylene oxide moiety,
 78 A. M. AL-SABAGH ET AL.

TABLE 2
IUPAC name and abbreviation of some representative compounds
Product
Structures and IUPAC name code Product nature

CH3 ---ðCH2 Þ7 ---CH ¼ CH---ðCH2 Þ7 CO---NH---CH2 --- I2 Amide

N-diethylene
CH2 ---NH---CH2 ---CH2 ---NH2
triamine cis-9-octadecenamide (main amide derived from pure oleic
acid and DETA)
CH3 ---ðCH2 Þ7 ---CH ¼ CH---ðCH2 Þ7 CO---
N-triethylene II2 Amide
NH---ðCH2 ---CH2 ---NHÞ2 ---CH2 ---CH2 ---NH2
tetraamine cis-9-octadecenamide (main amide derived from pure
oleic acid and TETA)
I 2Z Imidazoline
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2-(heptadeca-8-enyl)-4,5-dihydroimidazole-1-ethylamine
II2Z Imidazoline

2-(heptadeca-8-enyl)-4,5-dihydroimidazoline-1-diethyle-nediamine
I2ZE20 Ethoxylated imidazoline
(surfactant) EO ¼ 20

2-(heptadeca-8-enyl)-4,5-dihydroimidazoline-1-ethyl–N,N-dipolyoxyethylene
amine
II2ZE5 Ethoxylated imidazoline
(surfactant) EO ¼ 5
II2ZE10 Ethoxylated imidazoline
(surfactant) EO ¼ 10
II1ZE20 Ethoxylated imidazoline
2-(heptadeca-8-enyl)-4,5-dihydroimidazoline-1- (surfactant) EO ¼ 20
(N,N,N-tripolyoxyethylene)diethylene diamine
Where n ¼ x þ y, n ¼ x þ y þ z (n ¼ number of ethylene oxide units 5, 10, or 20).

an intense broad band at 3120–3610 cm1 for ethylene
oxide terminal hydroxyl group and an amide carbonyl
absorption at 1624 cm1 were observed.
1
H NMR Spectroscopic Analysis
It is worth noting that all the prepared compounds even
those depending on oleic acid are mainly based on com-
mercial fatty acid products. In other words, their analysis
is quite difficult due to the presence of the multi-
component systems and other impurities.
Further elucidation for the chemical structure of the
prepared compounds was performed using 1H NMR spec-
troscopy. 1H NMR spectra for I3, I3Z and I2ZE20 are
shown in Figures 2a–2c.
Figure 2a for I2 shows two overlapped signals at d ¼ 5.15
and 5.33 ppm for the amidic proton and the double bond
protons, respectively. In Figure 2b for I2Z, two overlapped
triplets appeared in the range of d ¼ 3.74–3.86 ppm
corresponding to both methylenes of the imidazoline ring.
Besides, the intensity of the signal appeared at d ¼ 3.14 ppm
 ETHOXYALTED 4,5-DIHYDROIMIDAZOLINE SURFACTANTS
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FIG. 1. Fingerprint for FTIR spectrum of a) amide of I2, b) imidazo-
line of I2Z, and c) ethoxylated I2Z 20.
decreases due to the incorporation of a further amine
group. Figure 2c for I2ZE20, shows a highly intense signal
in the range of d ¼ 3.44–3.56 ppm attributed to the
methylene groups of ethylene oxide moiety and the imida-
zoline ring appeared in the same range of d ¼ 3.7–3.9 ppm.
The FTIR and 1HNMR justified the structures of amide,
imidazoline and ethoxylate of prepared surfactants.
Surface Active and Thermodynamic Properties of the
Prepared Surfactants
The performance of surfactants as corrosion inhibitors
is assessed by their surface activity which is largely related
to their adsorption properties at interface and other
parameters such as CMC, cCMC, Cmax and Amin. Also,
the existing equilibrium between the monomeric free
surfactant molecules diffusing or getting adsorbed on the
79
interface and micelles in the bulk of the continuous phase
is a phenomenon playing an important role through
studying the corrosion inhibition capacity of inhibitors.
Thus, the determination of some thermodynamic para-
meters such as Gibbs free energy of both micellization
and adsorption will give an idea of their performance.
Critical Micelle Concentration
Typical curves of surface tension (c) versus ln the surfac-
tant molar concentration (lnC) for the prepared surfactants
were obtained (Figure 3). At CMC the adsorbed surfactant
molecules perform a monolayer covering the whole sur-
face[23] and meanwhile, the surfactant molecules aggregate
into micelles with their lyophilic groups directed toward the
interior of the micelles and their hydrophilic groups direc-
ted towards the solvent (water). Micellization is, therefore,
a mechanism alternative to adsorption at the interface for
removing lyophobic groups from contact with solvent,
thereby reducing the free energy of the system.
The exact structure of the micelles is still disputed.
However, Hano et al.[24] referred the structure of the
micelle to be roughly spherical with an interior region con-
taining the hydrophobic groups of the surfactant mole-
cules, of radius approximately equals to the length of a
fully extended hydrophobic groups, surrounded by an
outer region containing the hydrated hydrophilic groups
and bound water. However, CMC values are affected
markedly in aqueous solution by the structure of the sur-
factant. Table 3 shows the variation of CMC as a function
of the number of EO units for the second series II. It can be
seen that, the CMC values decrease as the hydrophilic
character of the surfactant increases (i.e., increase in EO
units number). As an example the CMC values, for II2ZE5,
II2ZE10, and II2ZE20 are 1.5  104, 0.82  104, and
0.67  104, respectively. This may be due to the increase
of oxyethylene units leads to an increase in the total mole-
cular weight of the surfactant and consequently the area
occupied by the molecule at the aqueous=air interface
increases. Hence, the number of molecules required to
cause interface saturations is decreased and the process of
micellization commences earlier compared to the surfac-
tant having lower oxyethylene content. This speculation
is in accordance with a previous explanation.[25] Also, it
was suggested that[26,27] the geminal poly oxyethylene
chains linked to the same atom (nitrogen atom in our
study) never individually hold a random coil configuration,
but intertwist with each other and penetrate the aqueous
solution. Therefore, the CMC values decrease with increas-
ing the number of oxyethylene units, which is opposite to
the usual observation in single chain poly oxyethylenated
surfactants. On the other hand, the surface activity and
the structure of the adsorbed films are greatly influenced
by the chemical structure of the hydrophobic groups of
the surfactants namely, different chain length and=or
 80 A. M. AL-SABAGH ET AL.
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FIG. 2. Fingerprint for 1H NMR spectra of a) amide of I2, b) imidazoline of I2Z, and c) ethoxylated I2Z 20.

branching. Through this study, the hydrophobic chain hydrophobic group as a main component yields higher
length varied slightly being 18 carbon atoms as obvious CMC values compared with those having unsaturations.
from fatty acid composition of the selected oils. However, The CMC value for I1ZE20 is 3  104 (mol  dm3) while
Table 3 shows that the surfactants containing saturated those for I3ZE20, I4ZE20, and I5ZE20 are in the range of
 ETHOXYALTED 4,5-DIHYDROIMIDAZOLINE SURFACTANTS
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FIG. 3. c-ln C adsorption isotherm for a) II2ZE5, b) II2ZE10, and
c) II2ZE20.
1.3  104 to 1.5  104 (mol  dm3). This may be attributed
to relatively higher electrostatic repulsion between the
hydrophobic chains containing unsaturation than in case
of saturated ones. This higher repulsion provides a force
tending to increase the area per molecule which in turn
decreases the concentration required to saturate water=air
interface. Thus, micellization in bulk starts earlier in case
of unsaturated hydrophobes, that is, lower CMC values.
Regarding the surface tension at CMC (cCMC) listed in
Table 3, it is noticeable that their values are unaffected
by the change in poly oxyethylene chain length (as obvious
from the values of (cCMC) for the second group surfac-
tants). On the other hand, the hydrophobic part affects
(cCMC) being the lowest for the surfactants based on oleic
acid (viz., I2ZE20, II2ZE5, II2ZE10, and II2ZE20). This
may be attributed to more optimum surfactant-water inter-
action compared with surfactant-surfactant interaction.
81
In case of the surfactants based on ricinoleic acid which
obtained from hydrolysis of castor oil (viz., I5ZE20,
II5ZE10, and II5ZE20), the presence of polar hydroxyl
branches in the hydrophobic moiety may oppose the pre-
viously mentioned repulsion force. Thus, based on the
same rationalization, CMC will again increases. This is
obvious from CMC values for I5 ZE20, II5 ZE5, II5 ZE10,
and II5 ZE20 listed in Table 3 based on ricinoleic acid as
a main hydrophobic component when compared with
other surfactants containing only one, two, or three unsa-
turation bonds through the hydrophobic moiety.
This feature is adopted through the values of effective-
ness for the surface-tension reduction (IICMC) tabulated
in Table 3. It can be observed that IICMC values are higher
for oleic acid based surfactants than others.
Maximum surface excess concentration Cmax in mol=
cm2 calculated from Gibbs equation (above in the Experi-
mental section) is tabulated in Table 3. As a general trend,
Cmax decreases by increasing the number of EO units incor-
porated in the surfactant structure (as shown by the second
group surfactants). This may be due to the increase of the
total molecular weight of the surfactant as a result of the
increase in the number of EO units. Consequently, the area
occupied by the surfactant molecule at the water=air inter-
face increases. Hence, the number of molecules required to
cause interface saturation decreases, that is, a decrease in
the maximum surface excess concentration. This specula-
tion is in accordance with a previous explanation.[25]
The effect of increased number of double bonds in the
hydrophobic part has not been widely investigated. Here,
regarding Cmax values for I3ZE20, I4ZE20, and I5ZE20, it
is found that Cmax decreases with increasing the number
of double bonds. This is mainly controlled by geometrical
packing considerations of the surfactant molecules. The
previously stated increased repulsion between hydrophobic
chains with increased unsaturation suggests less molecular
packing. Hence, a decreased Cmax is logically expected by
increasing the number of double bonds from one through
three double bonds.
Also, the area per molecule (Amin) at the interface can be
calculated from the Cmax values. The packing geometry,
controlled by relative cross-sectional areas of hydrophobic
chain and head groups, plays a vital part in (Amin) values.
From the data presented in Table 3, Amin values increase
with increasing the number of EO units incorporated. This
may be attributed to the strong affinity of the hydrophilic
groups for water that there is a tendency for them to be
spaced out to allow as much water as possible to solvate
each head group. In other words, hydration tends to
increase the area. This feature is also adopted in CMC
values, where CMC values decrease with increasing EO
units number incorporated. On the other hand, the increase
in the number of double bonds through the hydrophobic
chains tends to cause an increase in Amin. This behavior
 82 A. M. AL-SABAGH ET AL.

TABLE 3
Surface properties of the prepared surfactants
Surfactant CMC  104 cmcP max C  1010 Amin
1
code cmcc (mNm ) (mol  dm3) 1
(mNm ) (mol  cm2) (nm2 molecule1)

I1ZE20 39 3.0 33 2.48 69.1

I2ZE20 39 3.3 33 2.03 81.7
I3ZE20 34 1.5 38 2.40 66.9
I4ZE20 40 1.5 32 2.31 71.8
I5ZE20 40 1.3 32 2.00 83.0
II2ZE5 34 1.5 38 2.85 58.2
II2ZE10 34 0.82 38 2.83 58.6
II2ZE20 33 0.67 39 2.81 59.0
II3ZE5 40 4.5 32 2.49 60.6
II3ZE10 39 2.7 33 2.47 67.2
II3ZE20 39 2.7 33 2.45 67.7
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II5ZE5 39 1.6 33 2.93 56.6

II5ZE10 39 1.2 33 2.79 59.4
II5ZE20 39 0.6 33 2.45 67.7

may be a result of increased electrostatic repulsion with
increased number of double bonds.
Some Thermodynamic Functions of the Surfactants
Standard free energy of micellization determines the
spontaneity of micellization. Direct measurements of the
excess free energy of micellar systems,[28–30] through
activity of a solute or a solvent are difficult to be measured
precisely[31] at concentrations below 0.01 mol=kg. Conse-
quently, most information on the standard free energy of
micellization DGmic has been obtained indirectly through
CMC determination.[32,33] DGmic may be calculated by
choosing the following expression:
DGmic ¼ RTð1 þ aÞ ln CMC
through all the prepared surfactants. This geminal struc-
ture is considered to be unfavorable to hydration.[32]
The free energy of adsorption DGad for the selected
surfactants was calculated via the following equation:[35]
DGad ¼ DGmic  0:6023 PCMC Amin
The obtained values are listed in Table 4. Analyzing the
obtained data, it was found that all DGad values are nega-
tive and they are more negative than DGmic values. This
TABLE 4
Thermodynamic parameters of adsorption for the prepared
surfactants

where: R is the universal gas constant (¼8.314 J=mol  k; Surfactant DGmic DGad DGad  DGmic.
T is the absolute temperature (¼t þ 273)  K; and a is the code (KJ mol1) (KJ mol1) (KJ mol1)
fraction of the counter ions bound by the micelle in case
I1ZE20 20.06 21.38 1.32
of ionic surfactant (a ¼ 0 for nonionic surfactants).
I2ZE20 19.82 21.4 1.62
This expression uses a hypothetical standard initial state
I3ZE20 21.80 23.3 1.58
for nonmicellar surfactant species at unit mole fraction x—
I4ZE20 21.8 23.1 1.38
with ions or molecules behaving as at infinite dilution and
I5ZE20 22.02 23.6 1.59
a standard final state (the micelle itself). Analyzing the free
II2ZE5 21.8 23.1 1.33
energy of micellization data (tabulated in Table 4), one can
II2ZE10 23.2 24.5 1.34
get that micellization process is spontaneous (DGmic < 0).
II2ZE20 23.7 25.0 1.38
The data shows also that the negativity of DGmic
II3ZE5 19.07 20.35 1.28
increases with increasing the number of EO units incorpo-
II3ZE10 20.31 21.6 1.33
rated. This behavior indicates that increased oxyethylene
II3ZE20 20.81 22.1 1.34
chain length favors micellization process. This observation
II5ZE5 21.55 22.67 1.12
is opposite to the usual observed increase in DGmic for sin-
II5ZE10 22.3 23.4 1.18
gle chain poly oxyethylene surfactants.[34] This feature is
II5ZE20 24.04 25.3 1.34
attributed to the geminal poly oxyethylene chains found
 ETHOXYALTED 4,5-DIHYDROIMIDAZOLINE SURFACTANTS
indicates that the adsorption at the interface is associated
with a decrease in free energy of the system, that is, adsorp-
tion process is more spontaneous. Also, the more negative
values of DGad indicate favorable adsorption to micelliza-
tion. This may be due to the effect of steric factor on inhi-
biting of micellization is more than its effect on adsorption.
The product of structural effect DGmic–DGad for the
selected surfactants are shown in Table 4. This positive
product values reflect that these surfactants are more read-
ily adsorbed at air=aqueous solution interface.[36] This in
turn could account for investigating these surfactants as
corrosion inhibitors in a subsequent article.
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[1] Debus, H. (1858) Ann., 107: 204.
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[2] Lawrence, S.A. (2004) Amines: Synthesis, properties and
applications; Cambridge, UK: Cambridge University Press.
[3] Richardson, F.B. (1992) Industrial Applications of Surfac-
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