Synthesis, surface active and thermodynamic parameters of novel quaternary ammonium salts

Article abstract of DOI:10.1007/s11743-012-1385-5

Reactions of octanol, nonanol, decanol, and dodecanol with epichlorohydrin were carried out in the presence of sodium hydroxide as a catalyst. The synthesized non-ionic surfactants were modified with triethanolamine. Surface activity at the water-air interface and electrical conductivity of the resulting surfactants at 10, 20, 30 and 40 °C were determined and thermodynamic parameters of micellization and adsorption were calculated. It was established that the synthesized quaternary ammonium salts have the ability to localize thin crude oil films on the water surface formed due to spill. AOCS 2012.

Full text of DOI:10.1007/s11743-012-1385-5

J Surfact Deterg (2012) 15:721–727
DOI 10.1007/s11743-012-1385-5
ORIGINAL ARTICLE
Synthesis, Surface Active and Thermodynamic Parameters
of Novel Quaternary Ammonium Salts
•
Ziyafaddin H. Asadov Ravan A. Rahimov
•
•
Gulnara A. Ahmadova Khuraman A. Mammadova
Received: 24 February 2012 / Accepted: 29 June 2012 / Published online: 15 July 2012
Ó AOCS 2012
Abstract Reactions of octanol, nonanol, decanol, and
dodecanol with epichlorohydrin were carried out in the
presence of sodium hydroxide as a catalyst. The synthe-
sized non-ionic surfactants were modified with triethanol-
amine. Surface activity at the water-air interface and
electrical conductivity of the resulting surfactants at 10,
20, 30 and 40 °C were determined and thermodynamic
parameters of micellization and adsorption were calcu-
lated. It was established that the synthesized quaternary
ammonium salts have the ability to localize thin crude oil
films on the water surface formed due to spill.
wetting [5], antielectrostatic [8] and other useful properties.
These surfactants find application in the oil industry, for
example, in enhanced oil recovery [9]. In addition to being
highly surface active, chloropropoxylate surfactants have
the ability to collect and disperse thin films on the water
surface [10, 11]. The authors [11] synthesized chloro-
propoxylates of the higher alcohols and investigated their
surface-active properties. They have indicated that these
ethers are capable of removing thin crude oil slicks off the
surface of water of various mineralization degrees. To
decrease toxicity of these covalent-chlorine-containing
reagents and to improve their water solubility they may be
reacted with nitrogenous bases, transforming covalent
chlorine to non-hazardous ionic ones. Indian researchers
[12] obtained highly surface-active agents by quaterniza-
tion of chloropropoxylates of C10–C15 higher alcohols,
synthesized at an equimolar ratio of the initial reactants,
with phe-gly dipeptide.
Keywords Cationic surfactant ꢀ Micellization ꢀ
Adsorption ꢀ Oil spill
Abbreviations
TEA
Triethanolamine
C8ETEA
C9ETEA
TEA salt of chloroxypropyl ether of octanol
TEA salt of chloroxypropyl ether of nonanol
In this submitted article, chloropropoxylates of C8–C10
and C12 higher alcohols were modified by triethanolamine,
obtaining new surfactants. The surface-active and ther-
modynamic parameters of these cationic surfactants were
determined.
C10ETEA TEA salt of chloroxypropyl ether of decanol
C12ETEA TEA salt of chloroxypropyl ether of dodecanol
Introduction
Experimental Procedures
Various cationic (including gemini-type) surfactants syn-
thesized on the basis of epichlorohydrin (ECH) possess
antimicrobial [1–5], biological activity [6], foaming [7],
Reagents and Instruments
1H-NMR and 13C-NMR spectra were recorded on a Bruker
TOP SPIN 300.13 and 75.46 MHz spectrometer with
chemical shift values (d) in ppm downfield from TMS
using D2O and CCl4 as solvents. IR spectra were recorded
on an FT-IR, Spectrum BX model spectrometer using KBr
disks.
Z. H. Asadov ꢀ R. A. Rahimov (&) ꢀ G. A. Ahmadova ꢀ
K. A. Mammadova
Institute of Petrochemical Processes of Azerbaijan National
Academy of Sciences, Hojaly ave. 30, 1025 Baku, Azerbaijan
e-mail: revan_chem@mail.ru
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J Surfact Deterg (2012) 15:721–727
CH2Cl
ECH is a product of the Organic Synthesis Factory
cat.
(Sumgayit, Azerbaijan) with 99.97–99.98 % purity. NaOH
is a product of Merck (Germany, C99 % purity). Trietha-
nolamine is of analytical grade (Merck, Germany, C98 %
purity).
H
2C CH
O
CH2Cl
R
OCH2
CH
O
H
R
OH +
Scheme 1 Synthesis of C8–C10
surfactants
, C12 alcohol ethers—nonionic
Surface-Tension Measurements
residue-81.26; alkalinity-16.0 mg-eq/L, total hardness-60.0
mg-equiv/L.
All the surface tension measurements were carried out
using deionized water to make the solutions. The solutions
kept at the desired temperature (in the dark) were measured
45 s after transfer to the thermostated measuring dishes.
The actual temperature within the dishes was controlled
prior to and after the measurement by means of a ther-
mocouple. Deviations from the desired temperature were
0.2 °C at temperatures below 30 °C and 0.5 °C above
it. The surface tension as a function of concentration was
measured at 10, 20, 30, and 40 °C using a drop volume
Traube stalagmometer (Russian Federation). For mixed
solutions, particularly at low surfactant concentrations, the
approach to equilibrium took several hours. The repro-
ducibility (including long equilibration times and/or con-
tamination effects) was 1 %.
Synthesis of C8–C10, C12 Alcohol Ethers and Their
Salts with TEA
C8–C10 and C12 alcohols were chloropropoxylated with
epichlorohydrin (Scheme 1) as follows. 0.1 mol of alcohol
was added to 0.001 mol of NaOH and stirred for 1 h at
room temperature. Then 0.1 mol of epichlorohydrin was
added and the reaction was carried out in a stainless steel
autoclave at 140–160 °C. The reaction was conducted
within 10–12 h.
The scheme of the reaction for obtaining the quaternary
ammonium salts of the alcohol ether is shown below
(Scheme 2). To 0.1 mol of alcohol ester, 0.1 mol of TEA
was added and their interaction was conducted for 12 h at
50–55 °C. The product obtained was washed with hexane
and then dried. The synthesized quaternary ammonium
salts are highly viscous liquids or solid substances.
The salt based on C8 alcohol ether and TEA (C8ETEA):
yield 68 %, yellow-brown in color, soluble in water and
partially soluble in ethanol and insoluble in carbon tetra-
chloride, hexane, benzene, acetone and isopropanol.
IR, cm-1: 3,268.5 c (OH), 3,021.5, 2,928.1 and 2,884.2
c (CH), 2,329.5 c (N?H), 1,646.0 d (NH), 1,453.7 and
1,374.4 d (CH), 1,248.2 c (C–N), 1,042.4 c (C–O).
The salt based on C9 alcohol ether and TEA (C9ETEA):
yield 71 %, brown in color, soluble in water, ethanol and
insoluble in carbon tetrachloride, hexane, benzene, acetone
and isopropanol.
Electrical Conductivity Measurements
Electrical conductivity measurements were performed for
different concentrations of quaternary ammonium salts
solutions in the temperature range 10–40 °C, using a
conductivity meter OK-102/1 (Budapest) type conduc-
tometer. The solutions were continuously stirred and
thermostated at 1 °C. The measured conductivity was
plotted as a function of the surfactant concentration, and
the critical micelle concentration (CMC) was taken at the
intersection of the two linear parts of the conductivity
curve by the least-squares method.
Water Types Studied
IR, cm-1: 3,341.9 c (OH), 2,923.9 and 2,854.4 c (CH),
2,356.9 c (N?H), 1,646.0 d (NH), 1,461.9 and 1,377.1 d
(CH), 1,250.9 c (C–N), 1,069.8 c (C–O). 1H NMR
(300.15 MHz, D2O), 0.79 (3H, CH3), 1.20–1.30 (CH2)x,
3.4 (2H, N–CH2), 3.7 (2H, O–CH2), 3.8 (H, O–CH), 3.9
(2H, CH2–OH), 4.9 (1H, OH). 13C {1H} NMR
(75.15 MHz, D2O and CCl4). 14.0 (CH3), 22.6–31.9
(CH2)x, 61.5 (N–CH2–CH), 63.5 (N–CH2), 65.8 (CH2–
OH), 70.2 (CH–O), 72.3 (O–CH2), 74.3 (O–CH2–CH–O).
The salt based on C10 alcohol ether and TEA
(C10ETEA): yield 72 %, brown in color, soluble in water,
ethanol and partially soluble in acetone and insoluble in
carbon tetrachloride, hexane, benzene and isopropanol.
IR, cm-1: 3,305.0 c (OH), 2,923.0 and 2,856.8 c (CH),
2,362.5 c (N?H), 1,648.8 d (NH), 1,455.4 and 1,374.4 d
In the experiments four kinds of water were taken: (1)
Distilled water. (2) Fresh water. (3) Caspian sea water
having the following physico-chemical characteristics and
composition: q20 = 1.0098 g/mL, pH = 7.7. The contents
of ions and other species (mg/L): Na?-2,650; K?-90; Ca2?
-
250; Mg2?-900; NH4?-0.15; Cl--500; SO42--2,800;
NO3--0.1; PO43--0.35; NO2--0.007; SiO2-0.5; petroleum
products -0.005 %; dissolved oxygen-8 mg/L, total hard-
ness-69.0 mg-equiv/L. 4. The layer water from Surakhany
oil field (near Baku) of such physico- chemical character-
istics: q20 = 1.040 g/mL, pH = 7.1. Chemical composition
(mg/L): Ca2?-2,280; Mg2?-690; SO42--2,640; Cl--49,900;
iodine (bound)-1,860; naphthenic acids-6.6; petroleum-28.0;
dissolved oxygen-6.0; suspended substances-360.0; dry
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J Surfact Deterg (2012) 15:721–727
723
Scheme 2 Interaction between
C8–C10, C12 alcohol esters and
TEA
CH2
CH
N(CH2-CH2-OH)3
CH2Cl
CH
Cl
+ N(CH2-CH2-OH)3
H
R
OCH2
O
H
R
OCH2
O
(CH), 1,283.8 c (C–N), 1,034.1 c (C–O). 1H NMR
(300.15 MHz, D2O), 0.85 (3H, CH3), 1.24–1.26 (CH2)x, 3.5
(2H, N–CH2), 3.64 (2H, O–CH2), 3.94 (2H, CH2–OH), 4.20
(1H, CH–OH), 4.9 (1H, OH). 13C {1H} NMR (75.15 MHz,
D2O and CCl4). 14.1 (CH3), 22.7–31.9 (CH2)x, 63.5–65.8
(CH2–CH2–OH, CH2–N), 72.1 (O–CH2).
The salt based on C12 alcohol ether and TEA (C12ETEA):
yield 76 %, dark-brown incolor, soluble inwater and partially
soluble in ethanol, acetone and insoluble in carbon tetra-
chloride, hexane, benzene and isopropanol.
IR, cm-1: 3,292.0 c (OH), 2,922.0 and 2,856.8 c (CH),
2,362.5 c (N?H), 1,646.0 d (NH), 1,454.9 and 1,374.4 d
(CH), 1,248.2 c (C–N), 1,045.1 c (C–O).
Study of Petroleum-Collecting and Petroleum-
Dispersing Capacities
Investigations of petroleum-collecting and dispersing
ability of chloropropoxylates of higher alcohols and their
salts with TEA were carried out on the example of Ramany
crude oil films (density and kinematic viscosity at 20 °C
are respectively 0.86 g cm-3 and 0.16 cm2 s-1; Absheron
peninsula, Azerbaijan) crude oil (thickness of the film
0.165 mm) and four types of water: distilled, fresh, Cas-
pian sea and Surakhany layer. In these experiments, a film
was formed by 1 mL of crude oil on the surface of 40 mL
water and then 0.02 g of the tested reagents were intro-
duced. The chloropropoxylates and their salt were used as
5 wt% aqueous solutions.
Fig. 1 Surface tension versus ln of concentration of C8ETEA in
aqueous solution at 10, 20, 30 and 40 °C
Petroleum-collecting and dispersing ability was estimated
bythecoefficientofcollection-K(the ratiooftheinitialareaof
petroleum film surface and the surface area of the petroleum
spot formed under the action of the reagent) within the time (s,
hour) of observation in the experiment.
Results and Discussion
Critical Micelle Concentration
Fig. 2 Surface tension versus ln of concentration of C9ETEA in
aqueous solution at 10, 20, 30 and 40 °C
The critical micelle concentrations (CMC) of the investi-
gated quaternary ammonium salts at 10, 20, 30, and 40 °C
were determined by plotting the surface tension (c) versus
lnC where C is a concentration (Figs. 1, 2, 3, 4). The CMC
was determined from intersection points in the (c) versus
the logarithm of concentration curves. The CMC values
shown in Table 1 were found to decrease with the number
of methylene groups (CH2) in the alkyl side chains grad-
ually increased from nonyl chain up to dodecyl chain.
From Table 1 it can be seen that for each of the studied
surfactants there was a gradual decrease in the surface
tension with increasing concentration of the solution up to
a certain level above which a nearly constant value was
obtained. Such constant values of surface tension (at
20 °C) were found to be 41.0, 37.7, 35.5 and 33.2 mN m-1
for the surfactants containing C8, C9, C10 and C12 hydro-
carbon chain, respectively.
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Fig. 4 Surface tension versus ln of concentration of C12ETEA in
aqueous solution at 10, 20, 30 and 40 °C
Fig. 3 Surface tension versus ln of concentration of C10ETEA in
aqueous solution at 10, 20, 30 and 40 °C
pure water (c0) is defined as the effectiveness (pCMC), and
expressed as
Conductometer Measurements
pCMC ¼ c0 ꢁ cCMC
ð3Þ
Typical plots of conductivity v versus concentration for
the quaternary ammonium salts were graphed at various
temperatures (10–40 °C). Conductivity increases with
increasing temperature and concentration of surfactant. The
ionization degree-a was calculated from the slopes of
the two linear parts of the conductivity curves according to
the relationship [13]:
For the synthesized salts the effectiveness values ranged
between 30.2 and 39.9 mN m-1. The increase in hydro-
phobic chain length had a positive effect on pCMC values.
The efficiency (pC20) is the negative of the logarithm of
concentration of the surfactant solution, which lowers the
surface tension 20 units. A more efficient surfactant pro-
duces a greater depression of the surface tension at CMC.
The quaternary ammonium salts obtained had a good sur-
face activity. Table 1 shows, in general, the decrease in
surface tension values at the CMC in homologous series.
The same behavior was also observed in the efficiency
values, pC20 (Table 1). Increasing the number of methy-
lene groups (–CH2–) along the hydrophobic chains
increased the hydrophobicity of the molecules, hence
hydrophobe interactions became enhanced which decreased
the surface tension. Elevating the temperature increased the
efficiency (pC20) of the synthesized quaternary ammonium
salts.
S2
a ¼
ð1Þ
S1
where S1 and S2 are slopes of the respective dependence
v = f (concentration of surfactant) below and above the
CMC. The values for counterion binding degree-b were
calculated according to the relationship (2) [13]:
S2
b ¼ 1 ꢁ a ¼ 1 ꢁ
ð2Þ
S1
Figure 5 shows the plot of electric conductivity versus
concentration of C12ETEA solution at various temperatures.
Asisevidentfromthisfigure,thegraphconsistsoftwostraight
lines. Their intersection point corresponds to the CMC. Its
value differs slightly from the one determined by surface-
tension measurements. In the same way the conductivity
versus concentration plots were obtained for C8ETEA,
C9ETEA and C10ETEA salts and on their basis the values of
counterion binding degree were calculated (Table 1).
Minimum Interfacial Area/Molecule and Maximum
Interfacial Excess Concentration
Table 1 indicates that the number of hydrophilic groups
plays an important role in determining the maximum sur-
face excess concentration (Cmax) and the area occupied per
molecule (Amin) at the aqueous solution-air interface.
Surface excess concentrations (C) in mol dm-3 were
calculated from the relationship:
Effectiveness (pCMC) and Efficiency (pC20)
The difference between surface tension of quaternary
C ¼ ð1=nRTÞðꢁdc=d ln CÞ
ð4Þ
ammonium salts solution at their CMC (cCMC) and that of
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J Surfact Deterg (2012) 15:721–727
725
Table 1 Surface activity parameters (temperature T; critical micelle
concentration CMC; cCMC equilibrium surface tension at the CMC;
minimum surface area Amin; degree of counterion binding to micelles
b) of the synthesized quaternary ammonium salts at 10, 20, 30 and
40 °C
effectiveness pCMC; efficiency pC20; maximum surface excess Cmax
;
2
Amin (A )
Cmax 9 1010
CMC 9 102
(mol/L)
p
(mN/m)
cCMC
(mN/m)
pC20
˚
Reagent
C8ETEA
T (°C)
b
(mol/cm2)
10
20
30
40
10
20
30
40
10
20
30
40
10
20
30
40
0.78
0.75
0.72
0.69
0.83
0.79
0.74
0.70
0.86
0.81
0.77
0.73
0.92
0.88
0.85
0.81
2.33
2.22
2.09
1.92
2.21
1.91
1.74
1.61
2.14
1.98
1.78
1.46
2.50
1.99
1.63
1.53
71.2
74.8
79.3
86.5
75.0
86.9
95.5
103.3
77.6
84.0
93.5
113.5
66.4
83.2
101.7
108.8
4.24
4.08
3.99
3.84
4.12
3.99
3.74
3.50
3.88
3.69
3.48
3.34
3.72
3.62
3.54
3.32
30.2
31.8
31.5
31.4
34.1
35.1
34.2
34.0
37.7
37.3
37.1
36.2
39.9
39.6
39.2
38.1
44.0
41.0
39.5
38.2
40.1
37.7
37.0
35.6
36.5
35.5
34.1
33.4
34.3
33.2
32.0
31.5
4.30
4.40
4.47
4.51
4.60
4.69
4.76
4.81
4.91
4.97
5.03
5.09
5.52
5.56
5.58
5.62
C9ETEA
C
10ETEA
12ETEA
C
The Cmax values were used to calculate the minimum
area (Amin, in nm2) of a molecule, at the aqueous solution/
air interface using the relationship:
Amin ¼ 1016=NCmax
ð5Þ
where N is Avogadro number (6.023 9 1023). The maximum
surface excess, Cmax, and the area per molecule, Amin, varied
with the molecule structure, showing a larger area per mole-
culewithincreasingalkylchainlengthwhichindicatesthatthe
molecules were less tightly packed at the air/water interface
for the flexible, longer alkyl chain surfactants [14].
Thermodynamic Parameters of Micellization
The thermodynamic parameters of micellization expressed
by standard free energies DGmic, enthalpies DHmic and
entropies DSmic of micellization for the investigated sur-
factants were calculated from the equations [15]
Fig. 5 The plots of electrical conductivity, v, against concentration
of C12ETEA at different temperatures. The error of electrical
conductivity value was 0.3 lS/cm
DGmic ¼ ð2 ꢁ aÞRT ln CMC
and
ð6Þ
where (-dc/dlnC) is the surface activity (slope of c vs lnC
plots at constant absolute temperature, T) and
R = 8.314 J mol-1 K-1. As is seen, a value of C depends
on surfactant concentration, but Cmax has a certain value at
CMC. The Gibbs pre-factor ‘n’ in the equation represents
the number of particles per surfactant molecule whose
surface concentration changes with change in the bulk
concentration of the surfactant. For monovalent ionic sur-
factant, n = 2.
ꢁDSmic ¼ ðdDGmic=dTÞ
and by using the values of DGmic at 10, 20, 30, and 40 °C,
DHmic values were calculated as
ð7Þ
DHmic ¼ DGmic þ TDSmic
Analyzing the thermodynamic parameters of micellization
listed in Table 2 we may conclude that micellization process
ð8Þ
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J Surfact Deterg (2012) 15:721–727
Table 2 Thermodynamic parameters of micellization (free energy of
micellization DGmic; entropy of micellization DSmic and enthalpy of
entropy of adsorption DSads and enthalpy of adsorption DHads) of the
synthesized quaternary ammonium salts at 10, 20, 30 and 40 °C
micellization DHmic) and adsorption (free energy of adsorption DGads
;
Reagent
C8ETEA
T (°C)
DGmic (kC/mol)
DGad (kC/mol)
DSmic (kC/mol K)
DHmic (kC/mol)
-3.05
DSad (kC/mol K)
DHad (kC/mol)
-1.25
10
20
30
40
10
20
30
40
10
20
30
40
10
20
30
40
-13.2
-13.6
-13.9
-14.3
-13.7
-14.0
-14.4
-14.8
-14.2
-14.6
-14.9
-15.3
-14.9
-15.2
-15.6
-16.0
-14.5
-15.1
-15.5
-15.9
-15.3
-15.9
-16.4
-16.9
-16.0
-16.4
-17.1
-17.8
-16.5
-17.2
-18.0
-18.5
0.0360
0.0470
C9ETEA
0.0366
0.0368
0.0388
-3.34
-3.79
-3.86
0.0552
0.0602
0.0700
0.32
1.12
3.32
C
10ETEA
12ETEA
C
is spontaneous (DGmic \0). Also, a decrease in the standard
freeenergybecomeslargerwithincreasinghydrophobicchain
length. This is due to the hydrophobic chains and their
repulsion bywater molecules which is the motivating factor in
micelle formation. Inspite oftheformation ofhydrogenbonds
and the attractionofheadgroups bywater molecules, the alkyl
chain-water molecules repulsion enforces the surfactant
molecules to pass into a less energetic state which is the
micelle form to reduce the mentioned repulsion.
The DSad values were all positive and slightly greater
than the DSmic values for the same surfactants. This may
reflect the greater freedom of motion of the hydrocarbon
chains at the planar air/aqueous solution interface com-
pared to that in the relatively cramped interior beneath the
convex surface of the micelle.
Table 2 shows the variation of adsorption parameters of
the synthesized quaternary ammonium salts at different
temperatures. The standard free energy change of adsorp-
tion (DGads) was found to be more negative than that for
the micellization process (DGmic), which refers to the
higher tendency of these quaternary ammonium salts to
adsorption at the air–water interface rather than micelli-
zation. The preference of adsorption is governed by the
thermodynamic stability of the molecules at the air–water
interface. The free energy change of adsorption per meth-
ylene group for the quaternary ammonium salts was found
to be 0.7–0.8 kC.
Thermodynamic Parameters of Adsorption
The DGad values were calculated by using the relationship
[15]
DGad ¼ ð2 ꢁ aÞRTlnCMC ꢁ 0:6023pCMCACMC
ð9Þ
The DHad and DSad were obtained from the relationships
corresponding to Eqs. (7) and (8).
Table 3 Petroleum-collecting and petroleum dispersing properties of quaternary ammonium salts against Ramany crude oil films
Surfactants
Distilled water
Fresh water
Sea water
Surakhany layer water
s, h
K
s, h
K
s, h
K
s, h
K
5 wt% solution
C8ETEA
102
165
165
165
12.2
102
165
165
165
15.2
15.3
24.3
Disp.
102
165
165
165
Disp.
Disp.
Disp.
Disp.
102
165
165
165
Disp.
Disp.
Disp.
Disp.
C9ETEA
12.3
C
C
10ETEA
12ETEA
Disp.
Disp.
K maximum values of petroleum collecting coefficient; s fixed time intervals
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Author Biographies
Acknowledgments The authors would like to thank the Institute of
Petrochemical Processes of National Academy of Sciences of Azer-
baijan for the financial support.
Ziyafaddin H. Asadov received his M.Sc. in chemical engineering
from Azerbaijan State Oil Academy (Baku) in 1972, his Ph.D. in
polymer chemistry from the Institute of Petrochemical Synthesis of
USSR Academy of Sciences (Moscow) in 1979 and his D.Sc. in
petrochemistry from the Institute of Petrochemical Processes (IPCP)
of Azerbaijan Academy of Sciences (Baku) in 1992. In 2003
Z. H. Asadov was awarded the title of Professor in Polymer Chemistry
by the Higher Attestation Commission from the President of
Azerbaijan. He is currently the head of the laboratory of surfactants
in IPCP. His research encompasses the area of polymeric and
oligomeric surfactants.
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