Synthesis and evaluation of novel cationic gemini surfactants based on Guava crude fat as petroleum-collecting and dispersing agents

Article abstract of DOI:10.1016/j.molliq.2016.05.083

Cationic gemini surfactants based on Guava fat mixed fatty alcohols and isolated fatty alcohols C₈, C₁₂, C₁₆, C₁₈ were synthesized. The surface properties and thermodynamic parameters of micellization process, of the new cationic gemini surfactants have been investigated. Furthermore, the petroleum-collecting and dispersing indices of obtained surfactants, in waters of varying salinity have been studied. The results revealed that the tendency of these surfactants toward adsorption process was more than its tendency micellization and show high petroleum-collecting and dispersing properties.

Full text of DOI:10.1016/j.molliq.2016.05.083

Synthesis and evaluation of novel cationic gemini surfactants based on Guava
crude fat as petroleum-collecting and dispersing agents
Mohammed Abo-Riya, Ahmed Tantawy, Wagdy El-Dougdoug
PII:
DOI:
Reference:
S0167-7322(15)30881-3
doi: 10.1016/j.molliq.2016.05.083
MOLLIQ 5897
To appear in:
Journal of Molecular Liquids
Received date:
Revised date:
Accepted date:
22 October 2015
23 May 2016
26 May 2016
Please cite this article as: Mohammed Abo-Riya, Ahmed Tantawy, Wagdy El-Dougdoug,
Synthesis and evaluation of novel cationic gemini surfactants based on Guava crude fat
as petroleum-collecting and dispersing agents, Journal of Molecular Liquids (2016), doi:
10.1016/j.molliq.2016.05.083
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ACCEPTED MANUSCRIPT
Synthesis and evaluation of novel cationic gemini
surfactants based on Guava crude fat as petroleum-
collecting and dispersing agents
Mohammed Abo-Riya*, Ahmed Tantawy*, Wagdy El-Dougdoug
Organic Chemistry Department, Faculty of science, Benha
University, Benha, Egypt
* Corresponding author:
Fax:+20133222578
Tel: +201027099499 - +201002248870
E-mail address: MOHAMED.ABORYA@fsc.bu.edu.eg
And
AHMED.TANTAWY@fsc.bu.edu.eg
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Abstract
Cationic gemini surfactants based on Guava fat mixed fatty alcohols and isolated fatty
alcohols C8, C12, C16, C18 were synthesized. The surface properties and thermodynamic
parameters of micellization process, of the new cationic gemini surfactants have been
investigated. Furthermore, the petroleum-collecting and dispersing indices of obtained
surfactants, in waters of varying salinity have been studied. The results revealed that the
tendency of these surfactants toward adsorption process was more than its tendency
micellization and show high petroleum-collecting and dispersing properties.
Keywords: Cationic gemini surfactants; Guava crude fat; surface properties; petroleum-
collecting and dispersing indices.
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Introduction:
The products based on vegetable oil have widespread uses in industry as they have
much preference on petroleum products, owing to they are derived from renewable resources,
nontoxic, easily biodegradable, inexpensive, and environmentally friendly [1-3]. Fatty acids
of vegetable oils are produced by hydrolysis of the triglycerides, followed by elimination of
glycerol moiety.
Gemini surfactants are one of the oil based products which consists of two amphiphilic
moieties, usually fatty chain, attached to each other by flexible or rigid spacer. It was noted
that gemini surfactants can show preferable properties than the commonplace surfactants [4–
6]. Recently, some gemini surfactants were synthesized, and a formidable number of reports
on their unusual physicochemical properties has been published [7].
Pollution of water by petroleum oil is a great problem facing our ailing environment.
This problem has significant impact on the marine environment and also on both birds, and
animals. Sources of such pollution include production operations and oil exploration, natural
seeps, tanker accidents, industrial discharge, atmospheric input, and urban run-off [8].
Surfactants are widely used for collecting and dispersing the thin films of petroleum on
water surface [9–12]. Many types of surfactants were synthesized and their usage as
petroleum-collecting and dispersing were studied. Such types include non-ionic surfactants
which allow a good efficiency of removal of oil leaks from the water surface [13-16]. Ionic
surfactants containing hydroxyl groups have a great potential to collect and disperse the
fluffy petroleum films from the water reservoirs surface [17, 18]. Moreover, quaternary
ammonium salts or complexes based on fatty acids and nitrogen-containing compounds have
a high activity in collecting and dispersing the spilled crude oil [19-25].
In this work, we synthesized a new type of cationic gemini surfactants from non-edible
oil as quaternary ammonium salt. Their surface activity and their collecting and dispersing
capacities were evaluated for use in collecting and dispersing the petroleum films from water
surface.
1. Experimental
2.1. Materials
Guava crud material was obtained from Kaha Company for food products and juices,
Egypt, Octadecyl, hexadecyl, tetradecyl, dodecyl, decyl and octyl alcohols, chloroacetic acid
and N,N,N',N'-tetramethylethylenediamine were obtained by Aldrich Chemical Company
(Germany).
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2.2. Instrumentation
Gas liquid chromatography (GLC) of Guava methyl ester was done by Perkin Elmer
Auto System XL gas chromatograph by using flame ionization Detector (FID) with fused
silica capillary column ZB-5 (60 m * 0.32 I, d). Helium flow rate was 1mL / min. The peaks
were identified by comparing it with chromatograms of standard fatty acid methyl esters
(sigma, USA) in National Research Centre, Dakki, Cairo, Egypt.
The infrared spectra of the prepared surfactants were run on FT-IR spectra recorded in
1
KBr on a thermo nicolet iS10 FTIR spectrophotometer. The H-NMR spectra were generated
with 400 MHz signal and 4,000 gauss magnetic field in deuterated (DMSO) and /or in
chloroform (CDCl3) as a solvent and tetramethylsilane (TMS) as an internal reference. The
surface tension values of surfactants solutions determined by a Kruss K6 tensiometer. The
synthesis of the target gemini surfactants is shown in Figure 2.
2.3. Synthesis of quaternary ammonium gemini surfactants:
2.3.1.Extraction of Oil
The dried and cleaned seeds were grinding. Using non polar such as n-hexanes the oil
was extracted and dried using anhydrous sodium sulfate. Using rotary evaporator, the solvent
was separated to offer the oil sample.
2.3.2.Composition of Fatty acids of Guava fat and its specification
Fatty acids as methyl esters were analyzed [26] via GLC and the composition and
chemical characteristics of Guava fat, such as iodine, acid and saponification values, and
unsaponifiable matter, were determined according to AOCS Methods [27] and are given in
Table 1. The obtained results were agreement with previous studies by El-Dougdoug et al. [28].
=Table 1=
2.3.3.Reduction of fatty acids
Fatty alcohols of Guava seeds fat were obtained by reduction of the corresponding
methyl ester mixture via lithium aluminum hydride (LAH) [29].
2.3.4.Synthesis of 2-chloroacetate derivatives.
Fatty alcohols, namely, octanol, dodecanol, hexadecanol, octadecanol and mixed Gawfa
fatty alcohols (Ia-e) (0.1 mol) and chloroacteic acid (0.1 mol, 9.45 gm) esterified separately in
the presence of 0.01% p-toluene sulphonic acid as a catalyst and toluene as solvent, till the
calculated amount of water (0.1 mol, 1.8 mL) was separated [30]. Using vacuum rotary
evaporator to remove the solvent and the excess residual materials were distilled off. All the
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synthesized esters (Ia-e) have the same structure formula but different in the alkyl chain length
and were characterized using IR, 1H-NMR and 13C-NMR analysis.
Octyl-2-chloroacetate (Ia) CH3(CH2)6CH2-OCOCH2Cl.
Colorless, viscous liquid, yield =89%. The IR spectrum of octyl-2-chloroacetate (Ia)
revealed that, characteristic bands at 2953, 2922 and 2853 cm-1 (C-H aliphatic fatty chain),
1740 cm-1 (C= O of ester); 1155 cm-1 (C-O). On the other hand, 1HNMR of the same compound
(Ia); gave signals at δ (ppm): 0.85 (t, 3H, terminalCH3), 1.26 (s, 14H, (CH2)5-), 1.65 (m,
2H,CH2CH2CH2-O), 4.04 (s, 2H, CH2-Cl) and 4.18 (t, 2H, CH2-O).
Dodecyl-2-chloroacetate (Ib)CH3(CH2)10CH2-OCOCH2Cl.
Yellow color, viscous liquid, yield =87%. IR spectrum of compound (Ib) showed
stretching bands at 2953, 2922, and 2853 cm-1 (C-H, aliphatic fatty chain), 1745 cm-1 (C=O of
ester), 1160 cm-1 (C-O). The 1HNMR spectrum of compound (Ib); showed δ (ppm): 0.85 (t, 3H,
terminal CH3-), 1.30 (s, 22H, (CH2)9-), 1.66 (m, 2H, CH2CH2-O), 4.07 (s, 2H, CH2-Cl), 4.20
(t, 2H, CH2-O).
Hexadecyl-2-chloroacetate (Ic) CH3(CH2)14CH2-OCOCH2Cl.
White color, solid, mp = 45 oC, Yield = 85 %. IR showed bands at 2953, 2920, and 2849
cm-1 (C-H, aliphatic fatty chain), 1748 cm-1 (C=O of ester), and 1212cm-1 (C-O).1HNMR δ
(ppm): 0.89 (t, 3H, terminalCH3-), 1.28 (s, 30H, (CH2)13-), 1.68 (m, 2H, CH2CH2-O), 4.06 (s,
2H, CH2-Cl), 4.20 (t, 2H, CH2-O).
Octadecyl-2-chloroacetate (Id) CH3(CH2)16CH2-OCOCH2Cl.
White color, solid, mp = 47 oC, Yield = 84 %. IR showed bands at 2954, 2921, and 2851
1
cm-1 (C-H, aliphatic fatty chain), 1749 cm-1 (C=O of ester), and 1213cm-1 (C-O). HNMR δ
(ppm): 0.89 (t, 3H, terminalCH3-), 1.28 (s, 30H, (CH2)15-), 1.68 (m, 2H, CH2CH2-O), 4.06 (s,
2H, CH2-Cl), 4.20 (t, 2H, CH2-O).
2.3.5.Synthesis of Novel Cationic Gemini Surfactants (CGS8, CGS12, CGS16, CGS18 and
CGSGuava):
Cationic gemini surfactants from precursors CGS8, 12, 16, 18 were synthesized
according to the literature [31]. 2-chloroacetate derivatives (18 mmol) is added to N,N,N',N'-
tetramethylethylenediamine (9 mmol, 1.35mL) dissolved in 35 mL of diethyl ether with stirring
at room temperature to afford dimeric surfactants. The reaction mixture was filtered and the
product was washed by diethyl ether. The yield range is from 85 to 93 %. The structures of the
obtained surfactants were proven by IR, 1H- and 13C-NMR spectra. Detailed spectral data are
given below:
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CGS8:1, 2-ethane bis (dimethyl2 -(octyloxy)-2-oxoethyl ammonium chloride):
White color, viscous liquid, yield =93%. IR spectrum of compound revealed that, stretching
bands at 2955, 2924, and 2853 cm-1 (C-H, aliphatic fatty chain), 1740 cm-1 (C=O of ester), 1155
cm-1 (C-O). 1H-NMR δ (ppm): 0.86 (t, 6H, 2 [CH3-CH2-]), 1.28 (s, 16 H, 2 [(CH2)4-]), 1.69 (p,
4H, 2 [CH2CH2CH2-O]), 2.53 (s, 4H, 2 [CH2CH2CH2-O]), 3.72 (s, 12H, 4 [CH3-N+]), 4.21 (t,
13
4H, N+-CH2-CH2-N+), 4.80 (t, 4H, 2 [CH2-O]), 4.93 (s, 4H, 2 [O=C-CH2-N+]). C-NMR δC
(ppm, DMSO): 15.32 ( 2 [-CH3 alkyl chain]), 23.43 (2 [CH2-CH3]), 25.72 ( 2 [ CH2-CH2-O]),
30.62-34.18 (-CH2- alkyl chain of fatty alcohol), 44.29 (4 [CH3-N+]), 51.74 (+N-CH2-CH2N+),
59.87 ( 2 [-CH2-C=O]), 66.11 (2 [-CH2-O]), 166.43 (2 [-CH2-C=O]).
CGS12: 1,2-ethane bis (dimethyl 2-(dodecyloxy)-2-oxoethyl ammonium chloride):
Yellowish white color, viscous liquid, yield =92%. IR: 2953, 2924, and 2854 cm-1 (C–H,
aliphatic fatty chain), 1741 cm-1 (C=O of ester), and 1180 cm-1 (C-O). 1H-NMR δ (ppm): 0.87
(t, 6H, 2 [CH3-CH2-]), 1.26 (S, 32 H, 2 [(CH2)8-]), 1.67 (m, 4H, 2 [CH2CH2CH2-O]), 2.53 (s,
4H, 2 [CH2CH2CH2-O]), 3.72 (s, 12H, 4 [CH3-N+]), 4.17 (t, 4H, N+-CH2-CH2-N+), 4.81 (t,
4H, 2 [CH2-O]), 4.91 (s, 4H, 2 [O=C-CH2-N+]). 13C-NMR δC (ppm, DMSO):14.21 ( 2 [-CH3
alkyl chain]), 22.43 (2 [CH2-CH3]), 25.22 (2 [ CH2-CH2-O]), 28.11-34.34 (-CH2- alkyl chain
of fatty alcohol), 43.31 (4 [CH3-N+]), 51.76 (+N-CH2-CH2N+), 60.39 (2 [-CH2-C=O]), 66.25
(2 [-CH2-O]), 166.23 (2 [-CH2-C=O]).
CGS16: 1,2-ethane
bis
(dimethyl
2-(hexadecyloxy)-2-oxoethyl
ammonium
chloride):Yellowish white color, viscous liquid, yield =92%. IR: 2953, 2924, and 2854cm-
1(C–H, aliphatic fatty chain), 1741cm-1 (C=O of ester), and 1180cm-1(C-O). 1H-NMR δ (ppm):
0.87 (t, 6H, 2 [CH3-CH2-]), 1.26 (s, 48 H, 2 [(CH2)12-]), 1.67 (p, 4H, 2 [CH2CH2CH2-O]),
2.53 (s, 4H, 2 [CH2CH2CH2-O]), 3.7 2 (s, 12H, 4 [CH3-N+]), 4.17 (t, 4H, N+-CH2-CH2-N+),
4.81 (t, 4H, 2 [CH2-O]), 4.91 (s, 4H, 2 [O=C-CH2-N+]). 13C-NMR δC (ppm, DMSO):14.21 (2
[-CH3 alkyl chain]), 22.43 (2 [CH2-CH3]), 25.22 (2 [ CH2-CH2-O]), 28.11-34.34 (-CH2-
alkyl chain of fatty alcohol), 43.31 (4 [CH3-N+]), 51.76 (+N-CH2-CH2N+), 60.39 (2 [-CH2-
C=O]), 66.25 (2 [-CH2-O]), 166.23 (2 [-CH2-C=O]).
CGS18: 1,2-ethane bis (dimethyl 2-(octadecyloxy)-2-oxoethyl ammonium chloride):
o
White color, solid, mp= 90 C yield =89%. IR: 2953, 2921, and 2851 cm-1 (C–H, aliphatic
1
fatty chain), 1749 cm-1 (C=O of ester), and 1213 cm-1 (C-O). H-NMR δ ppm: 0.87 (t, 6H, 2
[CH3-CH2-]), 1.25 (s, 56 H, 2 [(CH2)14-]), 1.64 (p, 4H, 2 [CH2CH2CH2-O]), 2.24 (s, 4H, 2
[CH2CH2CH2-O]), 3.72 (s, 12H, 4 [CH3-N+]), 4.07(t, 4H,N+-CH2-CH2-N+), 4.21(t, 4H, 2
[CH2-O]), 4.80 (s, 4H, 2 [O=C-CH2-N+]), (Figure 1a).13C-NMR δC (ppm, DMSO): 14.22 (2
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[-CH3 alkyl chain]), 22.43 (2 [CH2-CH3]), 25.22 (2 [ CH2-CH2-O]), 29-32.68 (-CH2- alkyl
chain of fatty alcohol), 43.78 (4 [CH3-N+]), 52.58 (+N-CH2-CH2N+), 61.54 (2 [-CH2-C=O]),
66.11 (2 [-CH2-O]), 165.22 (2 [-CH2-C=O]) (Figure 1b).
=Figure 1=
2.4.Surface properties:
2.4.1.Surface and Interfacial Tension Measurements:
Surface tension values were measured by Krüss (Model K 6) tensiometer with a
o
platinum–iridium ring [32]. Distilled water with 72 dyne/cm surface tension at 25 C used to
prepare 0.1 % weight solution. The values of surface tension were determined at least four
times and the average value was taken.
o
Interfacial tension was measured for surfactant–oil system at 25 C with a 0.1 % surfactant
solution. The value, at which the ring was separated at the interfacial surface between the two
layers, was measured as interfacial tension. The interfacial tension between the distilled water
and the paraffin oil used is 56.2 dyne/cm.
2.4.2.Krafft point:
The temperature at which 0.1 % surfactants solution becomes clear by heating is gauge
the aqueous solubility. The Krafft points of gemini surfactants were measured by gradually
heating of the surfactant solution until it became clear [33].
2.4.3.Emulsion stability:
Powerful stirring of a 10 mmole solution (10.0 mL) and 10 mL of light paraffin oil at
o
25 C and measuring the time desired for separate aqueous phase (9.0 mL). This time was
determined as the emulsion stability [34].
2.4.4.Foam Height:
A 100 ml of the surfactant solution (0.1 wt %) was strongly shaken for 10 seconds in a
o
500 mL graduated cylinder at 25 C. The foam height was measured (in mL) as the foam
height initially produced. [35].
2.4.5.Stability to hydrolysis:
In a thermostat at 40 ºC, 10 mL (10 mmole) surfactant with 10 mL of 0.05 N NaOH or
2 N sulfuric acid was poured. The stability to hydrolysis was indicates by the time of sample
solution takes to be clouded [36].
2.5. The petroleum-collecting and dispersing properties:
Petroleum-collecting and dispersing capacities of the gemini surfactants from
Guava crude fat in the solid state and in the 5% wt. water solution have been studied on
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the Red sea crude oil (density and kinematic viscosity at 20oC are respectively 0.84 g/cm3
and 0.13 cm2/s) from the oil fields in the south sina (Egypt). The synthesized surfactant
(0.02 g) or its solution was added to the surface of distilled, fresh and the red Sea water
(separately) in Petri dishes with a thin film (thickness 0.16–0.17 mm) of this petroleum.
The petroleum collecting coefficient (K) are calculated from the formula K = So/S, where
So is an area of the surface of initial petroleum film and S is an area of the surface of
herded petroleum. In the case of crude oil film dispersing, the water surface cleaning
degree (kd) is found at fixed times of measurements. Kd is calculated as the ratio of the
surface area of the oil at the peripheral part of the dish and the surface area of the initial
oil slick [20].
2. Results and discussion:
3.1. Synthesis
Guava seeds are considered as remnants of guava juice industries and it had no
economic value. Fatty substances in the seeds were extracted by using n-hexanes and
examined to determine the fatty acid compositions and its chemical characteristics. The fatty
acid composition was determined by using GLC as fatty acid methyl ester, from the data
obtained we can clearly see that the most fatty acids are saturated acids, about 95 %, for that
reason it called Guava fat. The mixed fatty acids were separated from its fat by the alkali
hydrolysis, and then converted to methyl ester. The corresponding alcohols were obtained by
the hydrogenation of these fatty acids methyl ester.
Cationic gemini surfactants were synthesized from different fatty alcohols as shown
in Figure 2. The fatty alcohols (C8, C12, C16, C18 and mixed Guava fatty alcohols) were
esterification with 2-chloroacetic acid, respectively. The quaternization process of these
esters was done by reaction with N,N,N',N'-tetramethylethylenediamine to give the
quaternary salts. All the synthesized cationic gemini surfactants (CGS8, 12, 16 and 18) have
been elucidated using spectroscopic tools as shown above.
=Figure 2=
Moreover, the physical characterization and the petroleum-collecting and dispersing of
cationic gemini surfactants, with different number of methylene groups, were investigated
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and listed in were investigated and listed in Tables 2, 3 and 4. Also the effect of the structure
on surface-active parameters was studied.
=Table 2=
3.2. Surface Properties
Surface-active properties measurements of the synthesized cationic gemini surfactants
were made to evaluate the surface activity of surfactants and the corresponding data are listed
in Tables 2 and 3. It indicates that the surface and interfacial tension of water are reduced by
addition the cationic gemini surfactants, this is because the migration of the surfactants
molecules to the surface due to a hydrophobicity of two fatty chain lengths in the gemini
surfactants molecules. The critical micelle concentration (CMC) is an important value in the
solution parameters; it can be specified from the slopes of surface tension versus the natural
logarithm of concentration plots, in which the suddenly change in the was taken as the CMC
(see Figure 3). From Table 3, all the examined cationic gemini surfactants have lower CMC
values, The CMC values decrease with increasing the alkyl chain length for CGS8 and
CGS12 as expected, it can be interpreted as an increase of the hydrophobic chain the
molecules easily migrate to the surface and the micelle formed at low concentration. On the
contrary, the CMC values increase by increasing the alkyl chain length for CGS16 and
CGS18; this may be attributed to the large size of the molecule makes it movement more
difficult and hardly migrate to the surface.
=Figure 3=
=Table 3=
The Πcmc is the effectiveness of surface tension reduction or the surface pressure was
determined from the plots of surface tension with logarithm of concentration, Πcmc is defined
as (Eq. (1)):
Πcmc= γ0 – γcmc
(1)
Where γ0 is the surface tension of pure solvent and γcmc is the surface tension of solution at
cmc. The maximum reduction in surface tension has been determined by Πcmc and as a result
Πcmc makes the effectiveness of the amphiphile direct to lower the surface tension of the
water [37]. The surfactants synthesized in present work (CGS8, CGS12, CGS16 and CGS18)
have been studied and show a greater ability to reduce surface tension of water; especially
CGS12 has a greater efficiency in decrease surface tension. However, γcmc increases and Πcmc
decreases with increases the length of chain except CGS12 which is in agreement with the
earlier report except CGS12 [38].
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The maximum surface excess quantity (Γmax) at the air/water interface can be studied from
the following Gibbs adsorption isotherm [39].
Γmax= - (dγ/d logC)T / 2.303nRT
(2)
where, R is the gas constant (equal to 8.314 J mol−1K−1); T is the absolute temperature;
dγ/dlogC is the slop below the cmc in the surface tension plots, n is a constant and depends
on the number of surfactant molecules adsorbed at the interface (assumed as 4 in our
calculation). Also the minimum area occupied by surfactant molecule at interface (Amin, in
nm2) has been computed by following relation (Eq. (3)), [40].
Amin = 1014 / Γmax NA
(3)
Where NA is Avogadro’s constant (6.022 × 1023mol−1), Amin. Table 3 reflects the packing
density of surfactant monomer at the air–water solution which is related to surface activities
of the cationic gemini surfactants. The Γmax value decreases while the Amin value increases
with the raising the methylene groups in chain length except CGS8 suggesting that the
surfactant with lower hydrophobicity has higher packing densities at air/water interface.
Similar trends were also observed for other cationic gemini surfactants where it was
mentioned that the lower alkyl chain can be vertical to the surface and not liable to fold at the
air/water interface, while the higher surfactant molecules show folding [41]. Also the
adsorption and micellization parameters of the prepared surfactants were studied using
Gibb’s adsorption equations [32, 42]:
Gmoic  2.303RT logCMC
(4)
Gaods  Gmoic  (0.06023CMC Amin )
(5)
Whereas ( Ga0ds ) is adsorption free energy and ( Gmoic ) is micellization free energy.
The adsorption free energy ( Ga0ds ) is the energy of transfer of 1 mol of gemini surfactant
solution to the interface, and the free energy of micellization ( Gmoic ) is the work required for
the micellization [44]. When (Gmoic ) and ( Ga0ds ) is permanently negative the surfactants
molecules tend to adsorb at the interface and form micelles in solution [45]. The (Gmoic ) and
(
Ga0ds ) values of the surfactants are showed in Table 3. It is noted that the (Gmoic ) and (
Ga0ds ) always have negative values, leading to the two processes are spontaneously. Also, it
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was noticed that the adsorption energies are higher negative than ( Gmoic ), reference to that
the surfactants tend to be absorbed at the interface more than micellization in the solution.
3.3. Krafft point:
The Krafft point’s results of the surfactants are found in Table 2. The Krafft points of
all cationic gemini surfactants within this study have been determined and found to be less
than 0 oC. This gives it the ability to be used at low temperatures.
3.4. Emulsion stability:
The emulsifying ability of the cationic gemini surfactants is display in Table 2. It shows
that all studied surfactants have good emulsifying power. In addition to that the time it takes
to separate the oil and aqueous phases increase as the fatty chain increase as expected [45].
3.5. Foam Height:
The foaming power of surfactants is an important phenomenon while it determines in
which types of applications it can be used. The foam height data are listed in Table 2; it
showed that all surfactants have a high foaming height. Moreover, the values of foam height
in general decrease by increasing the length of fatty chain.
3.6. Stability to hydrolysis:
All the synthesized cationic gemini surfactants have been exposed to acidic and basic
mediums to study its hydrolysis. While all the prepared surfactants have ester linkage which
is easily hydrolysis in basic medium, for that all compounds have a lower stability in a basic
medium, as shown in Table 2. On the other hand, all the surfactants examined under this
study exhibited good stability in an acidic medium. It is also show that the increase in lengths
of fatty chain leads to more stability to hydrolysis in both acidic and basic media.
3.7. Petroleum-collecting and dispersing properties of novel Gemini surfactants:
The surfactants were added in undiluted form and as 5% wt. water solutions. Figures
4a, b and c show the petroleum-collecting and dispersing abilities of the gemini surfactants.
Figure 4a and 4b show the petroleum oil film before and after the addition of reagent. While
Figures 4c show two different dispersion shapes of petroleum oil after addition of reagent.
The data were reported in Table 4 and it is clear that all synthesized gemini surfactants in
diluted and undiluted form offer better petroleum-dispersing action. Additionally, CGS18
and CGS16 gave high petroleum-dispersing properties in diluted and undiluted forms than the
other surfactants, whereas Kd is ranging from 93.1 to 97.2%, τ =166 h (in distilled, fresh and
sea waters), moreover the diluted form show a very high petroleum-dispersing effect than in
undiluted form (in diluted form Kd = 97.2 and 95.8%, τ=166 h in distilled water, Kd = 97 and
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95% , τ=166 h in the fresh water, Kd = 97.1 and 95.1% , τ =166 h in the sea water).
Interestingly, CGS12 exhibits high petro-dispersing properties in the first days (Kd =96.6%, τ
=55 h) as diluted form in fresh water more than distilled and sea water and the effect
converted to petroleum-collecting effect after two days (Kmax = 15.4 τ = 60-166 h). While the
undiluted form CGS12 showed high petroleum-dispersing effect in all types of water (in
distilled water Kd = 95.3%, τ =155 h, fresh water Kd = 95.6%, τ =100 h, sea water Kd =
95.4%, τ =100 h). CGS8 gave high petroleum–dispersing effect in fresh water both in diluted
and undiluted form, and was stable for long time, while it has a moderate effect in diluted
form in both distilled and sea water. Also CGSGuava in diluted and undiluted form in distilled,
fresh and sea waters gave highly effect if it compared with the last two surfactants (CGS8 and
CGS12) and the effect is stable for long time as observed in the Table 4. From all the results
obtained, it is noted that the strength of petroleum-dispersing properties depends on the
hydrophobic part whereas the effect increases with hydrophobic part increases. Finally, all of
the prepared gemini surfactants gave a good petroleum-dispersing effect and it can be used as
petroleum-dispersing agents especially CGS18, CGS16, CGS12 and CGSGuava
.
The synthesized cationic gemini surfactants have better petroleum-dispersing properties
comparing with the corresponding conventional surfactants studied before [23-25].
=Figure 4=
=Table 4=
3. Conclusion
Novel cationic gemini surfactants from Guava crude fat were synthesized and its
1
structures were elucidated using spectroscopic tools such as IR, H- and 13C-NMR spectra.
The synthesized cationic gemini surfactants offered high surface activity and have tendency to
adsorbed at the interface more than the micellization in the bulk of their solutions. It has been
found that found that the surface activity was affected by the change in the length of the
hydrophobic part present in these cationic gemini surfactants. On the other hand, most of the
synthesized surfactants show high petroleum-collecting and dispersing properties especially
CGS18, CGS16 and CGS12. It is remarkable that CGSGuava gave highly petroleum-dispersing
effect. We conclude that all synthesized surfactants can be used as petroleum-collecting and
dispersing agents.
Acknowledgment
The authors are greatly thankful to the Faculty of science, Benha University, Benha,
Egypt for financially supporting.
12

ACCEPTED MANUSCRIPT
References
[1] D. K. Salunkhe, J. K. Chavan, R. N. Adsule, S. S. Kadam, World oil seed chemistry,
technology and utilization, Van Nostrand Reinhold, New York. (1992)1-8.
[2] M. Bockish, Ed. Fats and oils handbook; AOCS Press, Champaign, Illinois. (1998) 5-44.
[3] W. I. A. El-Dougdoug, M. A. Riya, B. A. Mahy, Synthesis and Surface Active Properties
of Sulfonated Acrylate Esters Based on Al-Cedre Oil, J. Surfact. Deterg. 18 (2015) 681-
688.
[4] F.M. Menger, C.A. Littau, Gemini surfactants: synthesis and properties, J. Am. Chem.
Soc. 113 (1991) 1451–1452.
[5] F.M. Menger, C.A. Littau, Gemini surfactants: a new class of self-assembling, J. Am.
Chem. Soc. 115 (1993) 10083–10090.
[6] M., J. Rosen, Geminis, A new generation of surfactants, Chem. Technol. 23 (1993)30–
33.
[7] X. P. Liu, J. L. Zhang, Q. T. Gong, S. Zhao, J. Y. Yu, Synthesis and properties of a novel
class of anionic gemini surfactants with polyoxyethylene spacers, Colloids and Surfaces
A: Physicochem. Eng. Aspects 362 (2010) 39–46.
[8] V. S. Wilson, G.A. LeBlanc, Petroleum pollution, Rev. Toxicol. 3 (2000) 77–112.
[9] F. R. Engelhardt, Remote sensing for oil spill detection and response, Pure Appl. Chem.
71 (1999) 103–111
[10] K., Gaaseidnes J. Turbeville, Separation of oil and water in oil spill recovery operation,
Pure Appl. Chem. 71 (1999) 95–101.
[11] J. F. Robert, L. Alun, Oil spill dispersants, Pure Appl. Chem. 71 (1999) 27–42.
[12] R. Varadaraj, M. L. Robbins, J. Bock, S. J. Pace, Oil slick dispersants, U.S. Patent
(2000) 6,011,072.
[13] S. H. Feairheller, R. G. Bistline, A. J. Bilyk, R. L. Dudley, M. F. Kozempel, M. J.
Haas, A novel technique for the preparation of secondary fatty amides. III.
Alkanolamides, diamides and arylamides, J. Am. Oil Chem. Soc. 71 (1994) 863–866.
[14] H. Kolancilar, Preparation of laurel oil alkanolamide from laurel oil, J. Am. Oil Chem.
Soc. 81(2004) 597–598.
[15] Z. H. Asadov, R. A. Rahimov, N. V. Salamova, Synthesis of Animal Fats
Ethylolamides, Ethylolamide Phosphates and Their Petroleum-Collecting and Dispersing
Properties, J. Am. Oil Chem. Soc. 89 (2012) 505-511.
13

ACCEPTED MANUSCRIPT
[16] A. D. Aga-zade, Asadov ZH, Barzegar Zenus M, Akhmedova GA, The propoxylation of
tetradecyl and pentadecyl alcohols, Pet. Chem. 41 (2001) 357–363.
[17] Z. H. Asadov, Ahmadova, G.A.; Rahimov, R.A.; Mammadova, K.h.A.: Colloidal-
chemical parameters of petroleum-collecting and, dispersing surfactants based on
vegetable oil acid fractions and 2-(chloromethyl) oxirane. J. Korean Chem. Soc. 55
(2011) 1012–1017.
[18] Z. H. Asadov, Rahimov, R.A.; Poladova, T.A.; Nasibova, S.M.; Guliyev, A. D.;
Asadova, A. Z., Triethyllenetetramine-based novel cationic surfactants and their
complexes with anionic polyelectrolytes. J. Mol. Liq. 166 (2012) 44–48.
[19] Z. H. Asadov, R. A. Rahimov, S. M. Nasibova, G. A. Ahmadova, Surface Activity,
Thermodynamics of Micellization and Adsorption Properties of Quaternary Salts Based
on Ethanolamines and Decyl Bromide, J. Surfactants Deterg. 13 (2010) 459-464.
[20]Z. H. Asadov, A. H. Tantawy, I. A. Zarbaliyeva, R. A. Rahimov, Petroleum-Collecting
and Dispersing Complexes Based on Oleic Acid and Nitrogenous Compounds as
Surface-Active Agents for Removing Thin Petroleum Films from Water Surface, J.
Oleo Sci. 61 (2012) 621-630.
[21] A. H. Tantawy, Z. H. Asadov, A. H. Azizov, R. A. Rahimov, I. A. Zarbaliyeva, Synthesis of
New, Ecologically Safe and Efficient Oil Slick-Collecting and Dispersing Agents Based on Oleic
Acid and Its Propoxylation Products, Arab. J. Sci. Eng. 39 (2014) 5437–5444.
[22] Z. H. Asadov, Rahimov, R.A.; Ahmadova, G.A., Colloidal chemical parameters and
petroleum-collecting properties of chloroxypropylate surfactants based on
epichlorohydrine and carboxylic acid fractions of animal origin.Mater.. Res. Innov. 14,
327–331 (2010)
[23] Z. H. Asadov, A. H. Tantawy, I. A. Zarbaliyeva, R. A. Rahimov, G. A. Ahmadova, Surfactants
Based on Palmitic Acid and Nitrogenous Bases for Removing Thin Oil Slicks from Water
Surface, Chem. J. 2(2012) 136-145.
[24] Z. H. Asadov, A. H. Tantawy, I. A. Zarbaliyeva, R. A. Rahimov, Synthesis of New Surface-
Active Ammonium-Type Complexes Based on Palmitic Acid For Removing Thin Petroleum
Films From Water Surface, Egypt J. Pet. (EGYJP), 22 (2013) 261-267.
[25] H. M. Abd El-Lateef, V. M.Abbasov, L. I. Aliyeva, E. E. Qasimov, I. T. Ismayilov, A. H.
Tantawy, Application of Complex Surfactant Based on Cottonseed Oil as CO-Corrosion Inhibitor
and for Removing Thin Oil Slicks from Water Surface. Casp. J. of Appl. Sci. Res. 1(2012) 57-67.
14

ACCEPTED MANUSCRIPT
[26] B. V. S. K. Rao, P. Vijayalakshmi, R. Subbarao Synthesis of long-chain (E)-3-alkenoic
acids by the Knoevenagel condensation of aliphatic aldehydes with malonic acid, J. Am.
Oil Chem. Soc. 70 (1993) 297-299.
[27] D. Firestone, Official methods and recommended practices of the American Oil
Chemists Society. The fifth edition includes all changes 1993–1997, Edition Analytical
methods, Champaign-Illinois (1998).
[28] W. I. A. El-Dougdoug, M. H. M Ahmed, Synthesis and surface active properties of
Gawafa fats based amphoteric surfactants. J. Olaj Szappan Kozmetika 53 (2004) 63–67.
[29] S. P. Ligthelm, E. von Rudloff and Donald A. Sutton, Preparation of unsaturated
long-chain alcohols by means of lithium aluminium hydride: some typical members of the
series, J. Chem. Soc. (1950) 3187-3190.
[30] W. I. A. El-Dougdoug, A. A. Mohamoud, Synthesis and evaluation of surface active
properties for some anionic copolymeric surfactants based on fatty octylacrylate and
sulfated products of oxypropylated allyl alcohol, J. Pigment Resin. Technol. 3(2002)
148–154
[31]L. Massi, F. Guittard, R. Levy, Y. Duccini, S. Ge´ribaldi, Preparation and antimicrobial
behaviour of gemini fluoro surfactants, Eur. J. Med. Chem. 38 (2003) 519-523.
[32]N. A. Negm, F. Ahmed, S. M. Tawfik, M. Ahmad, H. H. Hefni, A. K. Manal, Synthesis,
Surface and Thermodynamic Properties of Substituted Polytriethanolamine Nonionic
Surfactants, J. Surfactants Deterg. 16 (2013) 333-342.
[33]C. Xue, H. Zhu, T. Zhang, D. Cao, Z. Hu., Synthesis and properties of novel alkylbetaine
zwitterionic gemini surfactants derived from cyanuric chloride, Colloids and Surf. A:
Physicochem. Eng. Aspects 375 (2011) 141–146.
[34]G.H. Sayed, F. M. Ghuiba, M. I. Abdou, E. A. Badr, S. M. Tawfik, N. A. Negm,
Synthesis, surface and thermodynamic parameters of some biodegradable nonionic
surfactants derived from tannic acid, Colloids and Surf. A: Physicochem, Eng. Aspects
393 (2012) 96-104.
[35]N.A. Negm, S.M. Tawfik, Characterization, surface properties and biological activity of
some synthesized anionic surfactants, J. Ind. Eng. Chem. 20 (2014) 4463-4472.
[36]M. M. A. El-Sukkary, A.A. El-Sawy, F. El-Dib, Synthetic detergents from crude rice
bran oil. Hung J Ind Chem 15 (1987) 417.
[37]J. Lah, C. Pohar, G. Vesnaver, Calorimetric study of miceliization of alkylpyrinium and
alkyltrimethylammoinium bromides in water, J. Phys. Chem. B 104 (2000) 2522–2526.
15

ACCEPTED MANUSCRIPT
[38] A. Bhadani, H. Kataria, S. Singh, Synthesis, characterization and comparative
evaluation of phenoxy ring containing long chain gemini imidazolium and pyridinium
amphiphiles, J. Colloid Interface Sci. 361 (2011) 33-41.
[39] T. Takeshita, T. Shimohara, S. Maeda, Synthesis of EDTA monoalkyl amide chelates
and evaluation of the surface-active properties, J. Am. Oil Chem. Soc. 59 (1982) 104–
107.
[40] A. L. d. Q. Baddini, S.P. Cardoso, E. Hollauer, J.A.d.C.P. Gomes, Statistical analysis of
a corrosion inhibitor family on three steel surfaces (duplex, super-13 and carbon) in
hydrochloric acid solutions, Electrochim. Acta. 53 (2007) 434–446.
[41]R. Zana, Dimeric and oligomeric surfactants. Behavior at interfaces and in aqueous
solution: a review, Adv. Colloid Interf. Sci. 97 (2002) 205-253.
[42] N. A. Negm, N. G. Kandile, I. A. Aiad, M. A. Mohammad, New eco-friendly cationic
surfactants: Synthesis, characterization and applicability as corrosion inhibitors for
carbon steel in 1 N HCl, Colloids and Surfaces A: Physicochem. Eng. Aspects 391(2011)
224– 233.
[43] D. Varade, T. Joshi, V.K. Aswal, P.S. Goyal, P.A. Hassan, P. Bahadur, Effect of salt on
the micelles of cetyl pyridinium chloride,Colloids Surf. A 259 (2005) 95–101.
[44] J. T. Davis, E. K. Rideal, Interfacial Phenomena, Academic Press, New York, (1963).
[45] Rosen M. J., Surfactant and interfacial phenomena, second ed. John Wiley, New York
(1989), 286–294.
16

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(a)
(b)
1
Figure 1: H-NMR (a) and 13C-NMR (b) spectra of 1,2-ethane bis (dimethyl 2- (octadecyloxy)-2-oxoethyl
ammonium chloride (CGS18)
17

ACCEPTED MANUSCRIPT
(CH2)n
First step:
(CH2)n
Toluene
O
C
Cl-CH2COOH
+
P-Toluene sulphonic acid
H3C
O
CH2Cl
Ia-e
H3C
OH
a..n= 3
b..n= 7
c..n=11
d..n=13
H3C
Second step:
CH3
(CH2)n
e..n=mixed fatty alcohols
N
O
C
+
H3C
O
CH2Cl
N
CH3
H3C
Ia-e
Diethylether
O
C
H3C
CH3
H2
C
O
O
N
2 Cl
CGS8
O
C
N
C
H2
CH3
H3C
,
O
C
H3C
CH3
H2
C
O
O
CH3
CH3
N
2 Cl
CGS12
O
C
N
C
H2
H3C
,
CH3
CH3
CH3
O
C
H3C
CH3
H2
C
O
N
2 Cl
CGS16
O
C
N
O
C
H2
H3C
CH3
and
O
C
H3C
CH3
H2
C
N
O
CH3
CH3
2 Cl
CGS18
O
C
N
C
H2
O
H3C
CH3
Scheme 1. Synthetic route of Novel Cationic Gemini Surfactants.
Figure 2: Scheme 1. Synthetic route of Novel Cationic Gemini Surfactants.
18

ACCEPTED MANUSCRIPT
Minimal adsorption
70
65
60
55
50
45
40
35
30
CGS18
CGS16
CGS8
CGS12
Aggregation and multiadsorption
-8.0
-7.5
-7.0
-6.5
-6.0
-5.5
-5.0
-4.5
-4.0
-3.5
-3.0
Log C (Mol/L )
Figure 3: Variation of surface tension with log cationic Gemini surfactants concentration in aqueous solution at
298 K
19

ACCEPTED MANUSCRIPT
(a)
(b)
(c)
Figure 4: Shape of petroleum film at water surface before addition of reagent (a), different collection shapes
after addition of reagent (b), different dispersion shapes after addition of reagent (dispersion of
petroleum) (c)
20

ACCEPTED MANUSCRIPT
Fatty acid composition of Gawfa fat
Chemical characteristics of Gawfa fat
Fatty acid
Peak area %
Saturated Fatty acids:
Octanoic (C8 :0)
12.51
Acid value
23.45
Decanoic (C10:0
)
01.89
26.54
03.33
19.99
31.03
Iodine value
10.89
Dodecanoic (C12:0
)
Saponification value
Unsaponifiable matter
197.40
002.03
Tetradecanoic (C14:0
)
)
Hexadecanoic (C16.0
Octadecanoic (C18.0
Unsaturated Fatty acids:
Octadecenoic (C18:1
)
)
04.54
Table 1: Fatty acids composition and chemical characteristics of Guava fat:
21

ACCEPTED MANUSCRIPT
Emu.
I.F.T
0.1%
(dyne/c
m)
Krafft
p.
Stab. to
Comp
ound
No.
Stab.
10 mmole
min :
Foam h.
0.1%
Stab. to Base
hyd.
Acid hyd.
Hrs.:
0.1%
0C
(mm)
min : Sec.
min.
Sec.
CGS8
8
<0
<0
4 : 10
360
290
6 : 31
8 : 15
00 : 45
02 : 34
CGS1
2
11
7 : 55
CGS1
6
12
13
9
<0
<0
<0
10 : 43
11 : 26
4 : 53
210
150
320
12 : 30
04 : 30
04 : 32
10 : 13
More than
one day
CGS1
8
More than
one day
GSGuav
a
Table 2: Surface properties of Cationic Gemini surfactants:
22

ACCEPTED MANUSCRIPT
CMCx10-5
Gmoic
(kJ mol-1)
Ga0ds
(kJ mol-1)
γCMC
ΠCMC
Γmax×1010
(mol cm-2)
Compounds
Amin (nm2)
(Mol/l)
(mN/m)
(mN/m)
1.0
0.16
3.16
6.3
43
35
47
49
29
37
25
23
0.5
0.54
0.52
0.64
0.85
-28.524
-33.064
-25.673
-23.964
-29.46
-34.21
-26.63
-25.13
CGS8
CGS12
CGS16
CGS18
3.20
2.60
1.95
Table 3: Some surface-active parameters of the synthesized cationic surfactants:
23

ACCEPTED MANUSCRIPT
Undiluted product
Fresh water
Diluted (5% wt. water solution)
Different
types oils
Distilled
water
Distilled
water
Sea water
Fresh water
Sea water
τ (h) K (kd) τ (h) K (kd) τ (h) K (kd) τ (h) K (kd) τ (h) K (kd) τ (h) K (kd)
0
80.7%
92.2%
0
7
92.2%
94.3%
0
91%
0
41%
94%
0
7
74%
0
7
92%
5-
5-
7-
95.2%
90.1%
93.9%
166
55
55
CGS
Guava
31-
10-
70
31-
70
-
-
96.5% 166
1.7
93.1%
95.3%
-
166 90%
95.9%
3.7
95.1%
100
0-
98.1%
10
0
4.8
0
0
3.5
97.2%
-
0-1
0-7 90%
20 92.3%
7-
55
7-
23-
95.5%
5-
5-
95.9%
97.2%
4.8
97%
-
CGS
18
100
166
166
166
60-
166
30-
97.1%
166
-
-
-
-
-
0-
10
0
0
95.1%
93.1%
95.3%
-
0
3.5
0-1
3.7
0-7 90%
20 92.3%
7-
55
7-
23-
166
5-
5-
92.9%
95.2%
3.1
95.5%
95.8%
-
95%
-
CGS
16
100
166
166
60-
166
30-
95.1%
166
-
-
-
-
-
0-
10
0-
10
0
5
0
10
93.2%
95.4%
-
92.3%
93.1%
95.2%
-
0
6.65
96.6%
15.4
-
0
90.2%
93.4%
95.2%
-
5-
15-
100
15-
55
5-
55
5-
15
6.65
95.6%
100
CGS
12
70-
166
60-
166
20-
166
10 93.2%
-
-
-
-
-
-
15-
95.3%
155
-
-
-
-
0-
0-
0
82%
0
94% 0-1 93.1%
84.2%
95%
0
92.7%
1.5
25
CGS
8
5- 95.3% 5- 94.2% 5- 94.3% 15- 94.9% 30- 97%
5- 93.8%
24

ACCEPTED MANUSCRIPT
50
49
45
20
120
-
166
-
75-
68-
55-
70
25-
49
88%
-
95.1%
-
80.5%
50%
93%
92%
-
-
-
-
155
100
80-
60-
-
-
-
-
166
100
Table 4: Petroleum-collecting and petroleum-dispersing properties of some novel Gemini
surfactants based on Guava crude fat:
25

ACCEPTED MANUSCRIPT
Graphical abstract
26

ACCEPTED MANUSCRIPT
Highlights

Novel cationic gemini surfactants have been successfully synthesized with high yields and
elucidated.


Surface-active properties were investigated.
Poterleum-collecting and dispersing properties of the synthesized cationic Gemini surfactants
were studied.

The synthesized surfactants show high petroleum-collecting and dispersing properties.
27