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Egyptian Petroleum Research Institute (EPRI), Nasr City 11727, Cairo, Egypt
ABSTRACT W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
The surface activity and thermodynamic properties for
eight low molecular weight nonionic co-polyester (PE)
surfactants have been investigated. Surface and interfacial tensions (IFT) of surfactants in aqueous solutions
were measured using the spinning drop technique. From
these measurements, the critical micelle concentration
(CMC), the surface pressure at CMC (YCMC), the
maximum surface concentration (max), the minimum
area/molecule at the aqueous solution/air interface
(Amin), the effectiveness of surface tension reduction
(PCMC), the alkane carbon number (nmin) and the IFT at
nmin (Ymin) were determined. The thermodynamic
parameters of micellization (DGmic, DHmic and DSmic)
and of adsorption (DGad, DHad and DSad) for these
polymeric surfactants were also calculated. Structural
effects on micellization and adsorption are discussed in
terms of these parameters. The results show that the DGad
values were more negative than DGmic values for these
compounds, so that they favored adsorption before the
micellization process. They exhibited IFT in the order of
103 to 104 mN/m against the thin alkane carbon
number range 69. This range seemed to be prefered for
* Correspondence to: A. M. Al-Sabagh, Egyptian Petroleum
Research Institute (EPRI), Nasr City 11727, Cairo, Egypt.
INTRODUCTION W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
For economic considerations and other factors,
laboratory evaluation studies should precede field
applications of any effective formulation of surfactant systems to be used for enhanced oil recovery
(EOR). Extensive work has been done to evaluate
most of the commercially available monomeric
surfactants for EOR applications. Polymeric surfactants as EOR agents have appeared in the technical
and patent literature [15]. Only a few of these
polymeric surfactants have been extensively studied. However, little reliable information on the
surface and thermodynamic properties of wellcharacterized, highly purified compounds of this
type is available [69]. In polymeric ethoxylated
compounds a generalized formula is often used
since a well-characterized structure is not possible.
The data on ethoxylated surfactants are even more
Received 28 June 1999
Revised 15 September 1999
Accepted 26 September 1999
EXPERIMENTAL W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
Eight low molecular weight water-soluble polyester surfactants were prepared by reacting resercinol
with
chloroacetic
acid;
the
1,3dicarboxymethoxybenzene was precipitated with
dilute HCl. The polyesters were prepared by the
Copyright 2000 John Wiley & Sons, Ltd.
50 / Al-Sabagh
TABLE 1. Some Characterizations of the Investigated Polyester Surfactants
No. of
HLB
ethylene
oxide (n)
nn Ymin
(mN/
m) 103
20 C 30 C 40 C 50 C
1920
13
6.3
4.0
2320
17.6
6.8
1.0
3120
26.7
7.7
0.4
5120
49.6
8.6
0.9
Resorcinol maleic
anhydride-diol(PEG-400)
PE(M)13
1824
13
6.6
8.0
Resorcinol maleic
anhydride-diol(PEG-600)
PE(M)17.6
2224
17.6
7.2
1.0
Resorcinol maleic
anhydride-diol(PEG-1000)
PE(M)26.7
3024
26.7
7.9
0.6
Resorcinol maleic
anhydride-diol(PEG-2000)
PE(M)49.6
5024
49.6
8.8
0.8
Polymeric
polyester
surfactant
Designation
PE = polyester; (P) = polyester based on phthalic anhydride; (M) = polyester based on maleic anhydride;
diol = tetraethylene glycol; PEG = polyethylene glycol.
TABLE 2. Surface Excess, Area/Molecule and Effectiveness for the Polyester Surfactants
max (mol/cm2 1010)
PCMC (m N/m)
Surfactant
20 C
30 C
40 C
50 C
20 C
30 C
40 C
50 C
20 C
30 C
40 C
50 C
PE(P)13
PE(P)17.6
PE(P)26.7
PE(P)49.6
PE(M)13
PE(M)17.6
PE(M)26.7
PE(M)49.6
0.83
0.81
0.79
0.77
1.14
1.04
1.03
1.00
0.75
0.77
0.76
0.74
1.09
0.99
0.97
0.97
0.76
0.74
0.73
0.71
1.03
0.96
0.94
0.92
0.72
0.70
0.68
0.68
0.95
0.91
0.89
0.88
0.200
0.205
0.210
0.216
0.146
0.159
0.161
0.166
0.210
0.216
0.218
0.224
0.152
0.167
0.171
0.174
0.218
0.224
0.227
0.234
0.161
0.173
0.177
0.180
0.230
0.237
0.244
0.264
0.175
0.182
0.187
0.189
38.5
37.5
35.0
33.5
37.0
35.5
33.0
31.5
38.0
37.0
34.5
32.0
35.0
34.0
32.0
30.0
37.0
36.0
34.0
31.5
34.0
33.0
31.5
29.0
36.0
35.0
33.5
30.0
33.0
32.0
30.0
28.0
52 / Al-Sabagh
TABLE 3. Thermodynamic Parameters of Micellization and Adsorption for the Polyester Surfactants Based on Phthalic (P)
and Maleic (M) Anhydrid
Surfactant
PE(P)13
PE(P)17.6
PE(P)26.7
PE(P)49.6
PE(M)13
PE(M)17.6
PE(M)26.7
PE(M)49.6
Temp.
( C)
DGmic
(kJ/mol)
DHmic
(kJ/mol)
20
30
40
50
9.19
9.24
9.30
9.41
1.65
1.97
2.28
2.54
20
30
40
50
20
30
40
50
9.14
9.19
9.23
9.31
9.05
9.13
9.19
9.24
2.58
2.93
3.29
3.61
5.89
6.32
6.77
7.23
20
30
40
50
9.05
9.10
9.15
9.20
8.59
8.84
9.05
9.28
20
30
40
50
8.62
8.70
8.77
8.85
3.10
3.42
3.75
4.07
20
30
40
50
8.43
8.58
8.71
8.78
5.34
5.66
6.00
6.40
20
30
40
50
8.30
8.42
8.59
8.66
6.94
7.34
7.69
8.14
20
30
40
50
8.24
8.34
8.53
8.63
9.63
10.14
10.56
11.07
DSmic
(kJ/mol K)
0.037
0.040
0.051
0.060
0.040
0.047
0.052
0.061
DGad
(kJ/mol)
DHad
(kJ/mol)
14.20
14.50
14.85
15.00
18.41
19.27
20.27
21.14
14.00
14.25
14.45
14.65
13.68
14.07
14.12
14.35
21.30
22.36
23.47
24.45
24.61
25.73
26.85
27.83
13.35
13.66
14.17
15.00
27.67
28.76
29.65
30.34
11.87
11.90
12.07
12.33
32.08
33.55
34.80
36.12
11.83
11.99
12.15
12.29
37.98
39.52
39.36
40.92
11.50
11.72
11.95
12.04
38.31
39.79
41.26
42.87
12.00
12.35
12.51
12.90
44.39
45.79
47.29
48.97
DSad
(kJ/mol K)
0.11
0.12
0.13
0.14
0.15
0.17
0.18
0.18
1016
N
Table 3 lists standard free energies, DG0mic enthalpies, DH0mic, and entropies, DS0mic, of micellization for the four nonionic polyester surfactants
investigated based on phthalic or maleic anhydride
respectively (PE(P)n and PE(M)n). DG0mic values
were calculated by use of the relationship:
Gmic RT ln CMC
Gmic
Smic
T
54 / Al-Sabagh
[20, 30], indicating that a greater number of hydrogen bonds between polyoxyethylene chain oxygen
and water molecules are broken in the micellization
process as the number of oxyethylene units in the
molecule increases.
Thermodynamic Parameters of Adsorption
Table 3 lists free energies, DGad, enthalpies, DHad
and entropies, DSad, of adsorption DGad values
which were calculated by use of the relationship
Gad RT ln CMC 6:023 101 CMC ACMC 6
CONCLUSIONS W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W
The following conclusions are drawn:
(1) The PE(P)n (n = 13, 17.6, 26.7 and 49.6) reduce
the surface and IFT greater than PE(M)n
(n = the same number of ethylene oxide).
(2) The CMC for PE(P)n are smaller than the CMC
for PE(M)n.
(3) All investigated polyester surfactants favor the
adsorption process before the micellization
process.
(4) Both PE(P)n and PE(M)n give minimization of
IFT in range of 103 to 104 mN/m, and nmin
lies between 6 and 9 which favors polymeric
flooding in the area of enhanced oil recovery.
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