JJC Jordan Journal of Chemistry Vol. 5 No.2, 2010, pp.

175-189

The Inhibiting Effects of Alkyl Benzene Sulphonate and the

Magnetic Field on Aluminum Corrosion in Acidic Solution
A. K. Maaytaa, N. A. F. Al-Rawashdeha,b*
a
Chemistry Department, Jordan University of Science & Technology, P.O. Box 3030, Irbid-22110, Jordan.
b
Department of Chemistry, College of Science, United Arab Emirates University, P.O. Box 17551, Al Ain,
Abu Dhabi, UAE. Tel:+971-3-7134184; Fax: +971-3-7671291; E-mail: nathir@uaeu.ac.ae

Received on Jan. 19, 2010 Accepted on April 15, 2010

Abstract
Corrosion inhibition of aluminum (Al) in hydrochloric acid (HCl) by linear alkyl benzene
sulphonate (LABS) in the presences and absences of external magnetic field has been studied
using weight-loss and hydrogen evolution methods. Magnetic field of 0.1 T was applied. The
inhibition action depends on the chemical structure and the concentration of the inhibitor, the
concentration of the corrosive medium, the temperature, and the presence of an external
magnetic field. The percentage inhibition efficiency (%IE) of aluminum corrosion with LABS is
slightly increased in the presences of an external magnetic field. Results of weight loss method
are highly consistent with those obtained by hydrogen evolution method and both indicate that
the %IE increases with increasing inhibitor concentration, and the presence of external magnetic
field. The %IE decreases as the concentration of HCl increases. For the tested additives, an
increase in the temperature was found to decrease the %IE.
Keywords: Aluminum; Weight loss; Hydrogen evolution; Acidic corrosion; Magnetic field.
Introduction
From a purely thermo-dynamical point of view aluminum is an active metal.
However, in oxygen containing environment (air, water), aluminum is rapidly covered
[1]
with a dense inert oxide layer . The thickness of the oxide layer may vary as a
function of temperature and environment. Oxide films formed in air at room
temperature are 2-3 nm thick on pure aluminum. Heating to 425 °C may give films up
[2]
to 20 nm . If the oxide film is damaged, e.g. by a scratch, new oxide will immediately
[3]
form on the bare metal . This way aluminum is given excellent corrosion protection.
Aluminum has a natural corrosion protection from its oxide layer, but if exposed to
aggressive environments it may corrode. The following factors may affect the stability
of the aluminum oxide and thereby cause corrosion: (i) the oxide is not stable in acidic
[1]
(pH < 4) or alkaline (pH > 9) environments , (ii) aggressive ions (chlorides, fluorides)
may attack the oxide locally, and (iii) presence of certain elements (Ga, Tl, In, Sn, Pb)
[4]
may become incorporated in the oxide and destabilize it . Furthermore, corrosion
may occur to an aluminum surface coated with an organic material which is considered
as a localized corrosion and called filiform corrosion. This type of corrosion takes the
form of randomly distributed thread-like filaments, and is sometimes called vermiform
or warm track corrosion. Aluminum is susceptible to this type filiform corrosion in a

* Corresponding author: Tel. +971-3-7134184,, Fax: +971-3-7671291, E-mail: nathir@uaeu.ac.ae

175
relative humidity range of 75 to 90% with a temperature between 20 to 40 °C. Typical
filament growth rates average is about 0.1 mm/day. Filament width varies with
increasing humidity from 0.3 to 3 mm.
The depth of penetration in aluminum can be as deep as 15 µm. Numerous
coating systems used on aluminum are susceptible to filiform corrosion, including
nitrocellulose, epoxy, polyurethane, alkyd, epoxy and vinyls. Condensates containing
chloride, bromide, sulphate, carbonate and nitrate ions stimulate filiform corrosion [5].
Several groups of organic compounds have been reported to exert inhibitive
effects on the corrosion of aluminum. However, the protective activity afforded
generally has been poor. The extent of adsorption of an inhibitor depends on many
[6]
factors : (a) the nature and the surface charge of the metal; (b) the mode of
adsorption of the inhibitor; (c) the inhibitor’s chemical structure; and (d) the type of the
aggressive solution. The presence of heteroatoms (such as: oxygen, nitrogen, sulfur,
phosphorus), triple bonds, and aromatic rings in the inhibitor’s chemical structure
enhance the adsorption process. It has been reported that the inhibition efficiency (I%)
of heterocyclic organic compounds follows the sequence: oxygen < nitrogen < sulfur <
phosphorus [7-9].
Corrosion of aluminum and its alloys has been the subject of numerous studies
due to their importance in the recent civilization. Accordingly, numerous studies on the
[10-14]
inhibition of aluminum corrosion using organic substances have been conducted .
Recent studies have shed light on the effects of sulfur-containing compounds such as
thiourea and its derivatives on the inhibition of aluminum corrosion [15, 16].
Magnetic field usually affects the magnetic species each according to its nature
(ferromagnetic, paramagnetic or diamagnetic); one expects that chemical reactions
involving such species will be affected if a magnetic field is applied. Moreover,
elementary physics shows that charged particles in motion, such as ions, will be
subjected to Lorenz force caused by the application of a magnetic field. Lorenz force is
proportional to the charge of the ion (q), to its velocity (ν) and to the magnetic field (B),
ρ ρ ρ
taking directions into consideration, through the following equation F = qv × B , and

meaning that positive ions and negative ions moving in the same direction will be
affected by forces in opposite directions depending on the sign of (q). Moreover the
force should be perpendicular to both v and B.
Charged chemical species in a solution will have Brownian motion caused by
thermal energy. When these particles are subjected to an external magnetic field, their
motion will be affected and will be organized accordingly. Little work has been done on
the effect of magnetic field on chemical reactions [17-21].
In the present work, the weight loss method and the hydrogen evolution method
both were applied to investigate the inhibition of aluminum corrosion by linear alkyl
benzene sulphonate (LABS) and by applying externally applied magnetic fields.

176
Experimental
Pure aluminum (99.95%) was supplied in the form of sheets (Aldrich). The
organic inhibitor linear alkyl benzene sulphonate (LABS) (purity 97%) was supplied by
sulphochemical company-Jordan and was used as received. All solutions were made
up from Analar hydrochloric acid in triply distilled water. Before measuring, all tested
aluminum samples were mechanically polished using emery paper 800, degreased
with acetone, washed with distilled water, dried in alcohol and ether, and then weighed
using Electronic Semimicro Balance Sartorius 2024 MP6 with precision of ±0.01 mg.
The weight loss experiments were carried out using metallic aluminum sheets
having the dimensions (30 x 10 x 0.5 mm, exposed total area = 6.4 cm2), weighed and
immersed for 1 hr in 10 ml of Analar HCl solutions (2.0-3.5 M) containing different
concentrations of LABS (200-1000 ppm). After testing all samples were rinsed
thoroughly with triply distilled water, dried, and weighed again. The measurements
were carried out at different temperatures (303-333 K) using a water thermostat
controlled to ±0.5 K. To study the effect of magnetic field on corrosion using weight
loss method, same experimental procedure was repeated in the presence of an
externally applied magnetic field (0.1 T). The magnetic field was measured by Holl-
Probe, Leybol-Heraeus. Prior to experiments; all the solutions were deaerated by
passing nitrogen gas for 15 min. Scheme 1 shows the experimental setup of the
corrosion in the flux of magnetic field.
Test tube

N S

Al sheet

Scheme 1: Magnetic Field Experimental Setup.

The amount of hydrogen evolved from the corrosion reaction of aluminum was
measured using a homemade experimental setup (Scheme 2).

177
 Glass U-tube

Rubber
stopper

Graduated Test tube

cylinder

Water Metal sheet

container

Rubber tube

Scheme 2: Hydrogen evolution setup

Results and Discussion

Variation of aluminum weight loss in various concentrations of HCl at 333 K, in
absence and presence of external magnetic field (0.1 T) are shown in Figure1. Figure
1 shows that the weight loss values (mg) of aluminum increased as the concentration
of HCl increased. Remarkably, in the presence of externally applied magnetic field (0.1
T) the weight loss value is lower, especially at higher concentrations of HCl. The
magnetic fields decelerate the rate of corrosion of aluminum sheets in acidic medium
at a 333 K, which is in contract to what have been observed at 298 K. In a previous
study it has been observed that the magnetic fields accelerate the rate of corrosion of
aluminum sheets in acidic medium at 298 K [21].

178
 240.0

0T
220.0 0.1 T

200.0
Weight loss (mg)

180.0

160.0

140.0

120.0

100.0
1.5 2 2.5 3 3.5 4
[HCl] / M

Figure 1: The weight loss curves of aluminum in various concentrations of HCl at 333
K, in absence and presence of external magnetic field (0.1 T).
The weight loss curves of the aluminum sheets with addition of the inhibitor in
3.5 M HCl at various temperatures without and with externally applied magnetic fields
(0.1 T) are shown in Figures 2 and 3, respectively.

250.0
333 K
323 K
313 K
200.0 303 K
Weight loss (mg)

150.0

100.0

50.0

0.0
0 200 400 600 800 1000 1200

[LABS] / ppm

Figure 2: Effect of LABS concentration on weight loss (mg) in absence of external

magnetic field, at various temperatures. Immersion time 1 h, [HCl] = 3.5 M.

179
 250.0
333 K
323 K
313 K
200.0 303 K
Weight loss (mg)

150.0

100.0

50.0

0.0
0 200 400 600 800 1000 1200
[LABS] / ppm

Figure 3: Effect of LABS concentration on weight loss (mg) in the presence of external
magnetic field (0.1 T), at various temperatures. Immersion time 1 h, [HCl] = 3.5 M.

The curves in Figure 2, without externally applied magnetic fields, show that the
weight loss values (mg) of aluminum in 3.5 M HCl solution containing LABS are
decreased as the concentration of the inhibitor increased, i.e. the corrosion inhibition
strengthened with the increase of the surfactant concentration. The trend of LABS in
externally applied magnetic fields (Figure 3) is similar to that observed without
externally applied magnetic fields but with slight reduction in weight loss at all
temperatures. In addition, the curves in Figures 2 and 3 show that when the
concentration of the tested surfactant is greater than 600 ppm, the weight loss of
aluminum does not change remarkably, this trend was observed at all temperatures.
[22]
The critical micelle concentration (CMC) of LABS is 650 ppm . In another word,
when the concentration of surfactant reaches its CMC value, the adsorbed amount of
inhibitor and its coverage to the aluminum's surface reached maximum value. The
results obtained reveal that the weight loss of aluminum in the presence of a magnetic
field was less than that in the absence of a magnetic field at the same concentration
range of the inhibitor. Thus, an applied magnetic field appeared to assist the rate of
[19]
passivation (formation of Al2O3) on the surface . The results obtained were in
[18,19]
agreement with previously published results of aluminum and iron . One of the
[23]
magnetic field effects was due to the Lorentz force . The effects of temperature and
concentration of the inhibitor on weight loss of aluminum in HCl in the absence and
presences of magnetic field have been studied, and the results of these effects were
summarized in Figures 4 and 5. It's remarkably from these figures that as temperature

180
increases the weight loss increases due to the higher dissolution of aluminum at higher
temperature. Furthermore, for the concentration of the tested surfactant above the
CMC (650 ppm), the weight loss of aluminum does not change remarkably.

200.0
200 ppm
180.0 400 ppm
600 ppm
800 ppm
160.0 1000 ppm
Weight loss (mg)

140.0

120.0

100.0

80.0

60.0

40.0
300 305 310 315 320 325 330 335

T/K

Figure 4: Variation of weight loss (mg) with temperature at various concentrations of

LABS, in the absence of magnetic field. Immersion time 1 h, [HCl] = 3.5 M.

180.0
200 ppm
400 ppm
160.0 600 ppm
800 ppm
1000 ppm
140.0
Weight loss (mg)

120.0

100.0

80.0

60.0

40.0
300 305 310 315 320 325 330 335
T/K

Figure 5: Variation of weight loss (mg) with temperature at various concentrations of

LABS, in the presence of magnetic field (0.1 T). Immersion time 1 h, [HCl] = 3.5 M.

181
 The loss in weight of the aluminum sheets in the presence of the tested inhibitor
(LABS) at various concentrations (200 to 1000 ppm) was determined in different HCl
concentrations and temperatures. At each concentration of the inhibitor, the
percentage inhibition efficiency (% IE) is calculated using the relationship [24]:

Wu − Wi
%IE = x100% (1)
Wu

Where Wi and Wu are the weight loss with and without the inhibitor, respectively.
Figures 6 and 7, shows the variation in %IE of LABS according to its concentration in
3.5 M HCl at various temperatures in the absences and presences of a magnetic field,
respectively. The results show less inhibition efficiency of LABS in absences than
presences of magnetic field. All tests show a slight decrease in the %IE with increasing
temperature, but the inhibitive effect still persists even at higher temperature (333 K).
This behavior indicates that the adsorbed molecules formed a barrier film on the
aluminum surface [25].

80.0

333 K
323 K
70.0 313 K
303 K

60.0
% IE

50.0

40.0

30.0

20.0
0 200 400 600 800 1000 1200
[LABS] / ppm

Figure 6: Variation of inhibition efficiency (%IE) with LABS concentration in 3.5 M HCl
in the absences of magnetic field at various temperatures.

182
 80.0

333 K
323 K
70.0 313 K
303 K

60.0
% IE

50.0

40.0

30.0

20.0
0 200 400 600 800 1000 1200
[LABS] / ppm

Figure 7: Variation of inhibition efficiency (%IE) with LABS concentration in 3.5 M HCl
in the presences of magnetic field (0.1 T) at various temperatures.

The effect of external magnetic field, inhibitor, and temperature on the hydrogen
evolutions of the corrosion of aluminum sheets in HCl are shown in Figures 8-12. The
results of these figures emphasize the observations obtained by weight loss
measurements, where it can be concluded that the presences of inhibitor and external
magnetic field is needed to increase the inhibition of corrosion of aluminum in acidic
medium.

183
 260.0

0T
240.0
0.1 T

220.0
3
Volume of H / cm

200.0
2

180.0

160.0

140.0

120.0

100.0
1.5 2 2.5 3 3.5 4
[HCl] / ppm

Figure 8: The hydrogen evolution curves of aluminum in various concentrations of HCl

at 333 K, in absence and presence of external magnetic field (0.1 T).

300.0
333
323
250.0 313
303
3

200.0
Volume of H / cm
2

150.0

100.0

50.0

0.0
0 200 400 600 800 1000 1200

[LABS] / ppm

Figure 9: Effect of LABS concentration on hydrogen evolution curves in absence of

external magnetic field, at various temperatures. Immersion time 1 h, [HCl] = 3.5 M.

184
 300.0
333
323
250.0 313
303
3

200.0
Volume of H / cm
2

150.0

100.0

50.0

0.0
0 200 400 600 800 1000 1200

[LABS] / ppm

Figure 10: Effect of LABS concentration on hydrogen evolution curves in the presence
of external magnetic field (0.1 T), at various temperatures. Immersion time 1 h, [HCl] =
3.5 M.

220.0
200 ppm
400 ppm
200.0 600 ppm
800 ppm
180.0 1000 ppm
3
Volume of H / cm

160.0
2

140.0

120.0

100.0

80.0

60.0
300 305 310 315 320 325 330 335

T/K

Figure 11: Variation of hydrogen evolution curves with temperature at various

concentrations of LABS, in the absence of magnetic field. Immersion time 1 h, [HCl] =
3.5 M.

185
 200.0
200 ppm
400 ppm
180.0 600 ppm
800 ppm
160.0 1000 ppm
3
Volume of H / cm

140.0
2

120.0

100.0

80.0

60.0

40.0
300 305 310 315 320 325 330 335

T/K

Figure 12: Variation of hydrogen evolution curves with temperature at various

concentrations of LABS, in the presence of magnetic field (0.1 T). Immersion time 1 h,
[HCl] = 3.5 M.

Using the results of hydrogen evolution method obtained in absence and

presence of magnetic field (0.1T), the corrosion rate of aluminum is determined by
using the relation:

∆m
Wcorr = (2)
S ∗t

Where ∆m is the mass loss, S is the surface area aluminum sheet and t is the
immersion period.
Table 1 shows the corrosion rate and the percentage inhibition efficiency of the
inhibitor (LABS) at various concentrations (200-1000 ppm) in 2.5 M HCl in an
immersion period 1 hr, at 333 K. Closer inspection of Table 1 reveals that the inhibition
efficiency (%IE) increases with increasing inhibitor concentration, and in presence of
external magnetic field reaching a maximum inhibition efficiency of 37.89% at its
highest values.

186
Table 1: Corrosion rate (mg/cm2.h) and percentage inhibition efficiency of inhibitors at
various concentrations in 2.5 M of HCl at 333 K.
0.1 Tesla 0 Tesla
Inhibitor Conc. (ppm)
Wcorr %IE Wcorr %IE
Blank 22.03 ----- 23.51 -----
200 19.20 12.79 21.75 7.48
400 17.02 22.74 19.64 16.47
600 15.44 29.93 17.97 23.55
800 14.42 34.54 16.95 27.92
1000 13.68 37.89 16.22 31.02

Inspection of the data in Table 1 reveals that LABS appeared to act as inhibitor
over the studied concentration range. The corrosion rate values indicate that the
external magnetic field has a reasonable effect on the inhibition of aluminum in LABS.
The reduction in the dissolution of aluminum in the presence of LABS inhibitor may be
attributed to the sulphonate ion present in the functional group. It is obvious that the
inhibition effect of LABS increases with increasing its concentration and reaches a
value where the weight loss of aluminum does not change remarkably.
Reaching a limiting value in the weight loss is related to the formation of a
monolayer film on the adsorbate over the surface of the metal [26]. This phenomenon is
more likely to take place when the concentration of the surfactant is near its CMC. In
this study for the tested inhibitor, it has been observed that the weight loss did not
reached a limiting value (plateau) but only a remarkable decrease in the changes in
weight loss has been observed. This result indicates that the tested inhibitor (LABS)
does not form a complete monolayer film at the experimental conditions of this study.
When discussing inhibition action of surface-active agents various factors must
[27]
be taken into consideration . These include the number of functional groups taking
part in the adsorption of the inhibitor molecule and their electron charge density,
molecular size and geometry, mode of interaction, heats of hydrogenation and of
additives. Most likely, the adsorption of LABS occurs through the adsorption of the
sulphonate ion at the surface of the aluminum. Thus, due to steric effect of alkyl chain
the adopted spatial orientation of LABS on the metal surface doesn't allow the
formation of complete monolayer film.
It is known that passive metals corrode according to the so-called pitting
mechanism, which includes four main steps: breakdown of passivity, early stages of pit
[28]
growth, late stages of pit growth, and repassivation phenomena . The breakdown of
passivity may be caused by the mechanism of chloride penetration through the oxide
film; the passive layer breaking mechanism as well as the mechanism of chloride
adsorbed at the oxide surface and accelerated transfer of metal cations to the
electrolyte. The formation of micelle structure, which develops in a pit domain during its

187
growth, plays an essential part in these mechanisms. According to our results, we
suggest that the magnetic field could affect the structure of the repassivating deposits
of LABS. We came to the conclusion that under the influence of magnetic field the
initial LABS particles reorient themselves in such a way that the interaction energy
between the LABS micelles and magnetic field would become minimal. In addition, the
observed corrosion magneto inhibition effect could be explained in terms of field
assisted formation of the oxides with higher degree of dispersion. This effect was
evident from the decrease in mass loss.
Conclusions
The anionic surfactant tested (LABS) shows a reasonable inhibition for
aluminum corrosion in acidic medium in the presences and absences of external
magnetic field. Its ability as an inhibitor differs in the presences and absences of
external magnetic field. This is quite probably due to differences of mode of adsorption,
and the field-assisted formation of the deposited micelle with a superior capacity to pit
repassivation. The %IE increases with increasing inhibitor concentration and
decreasing the corrosive media concentration. In addition, there are quite increase in
the %IE in the presences of magnetic field. Thus, the presences of a magnetic field
suppress corrosion reactions of aluminum sheets with addition of the inhibitor in HCl at
various temperatures. The %IE decreases with increasing temperature as a result of
the higher dissolution rate of aluminum at higher temperatures.
References
[1] Pourbaix, M., NACE Cebelcor, Huston, 1974.
[2] Shimizu, K.; Furneaux, R. C.; Thompson, G. E.; Wood, G. C.; Gotoh, A.; Kobayashi, K.,
Oxidation of aluminium, 1991, 35, 427-439.
[3] Davis, J. R. et. al, editor, "Metals Handbook", Ninth edition, ASM International, Ohio,
1987, 13, 104-122 and 583-609.
[4] Hatch, J. E., editor. "Aluminium - Properties and physical metallurgy", pages 242-264.
ASM International, Ohio, 1984.
[5] De laet, J.; Terryn, H.; Vereecken, J., Electrochimica acta, 1996, 41, 1155-1161.
[6] Saleh, M.R.; Shams El Din , A.M., Corros. Sci., 1981, 12, 688.
[7] Tadros, A.B.; Abdenabery, A.B., J. Electroanal. Chem., 1988, 24, 433.
[8] Thomas, J.G.N., Some new fundamental aspects in corrosion inhibition, Proceedings. 5th
Europ. Symp. Corros. Inhibitors, Ferrara, Italy, 1980, pp.453.
[9] Donnelly, B.; Downie, T.C.; Grzeskowiak, R.; Hambourg, H.R.; Shori, D., Corros. Sci.,
1977, 18, 109.
[10] Abdel Kader, J.M.; Shams El Din, A. M., Corros. Sci., 1970, 10 , 551.
[11] Sampat, S. S.; Vora, J. C., Corros. Sci., 1974, 14, 591.
[12] Shalaby, L. A.; El Sobki, K. M.; Abdel Azim, A. A., Corros. Sci., 1979, 16, 637.
[13] El Mahdy, G. A.; Mahmoud, S. S., Corros. Sci., 1995, 51, 436.
[14] Al-Rawashdeh, N. A. F.; Maayta, A. K.; Ani-Corrosion Methods & Materials, 2005, 52,
160.
[15] Subramanyam, N.C.; Sheshardi, B.S.; Mayanna, S.M., Corros. Sci., 1993, 34 , 563.
[16] Maayta, A. K.; Al-Rawashdeh, N. A. F,. Corros. Sci., 2004, 46, 1129
[17] Shinohara, K.; Aogaki, R., Electrochem., 1999, 67,126.
[18] Chiba, A.; Kawazu, K.; Nakano, O.; Tamura, T.; Yoshihara, S.; Sato E., Corros.
Sci., 1994, 36, 539.
[19] Rucinskiene, A.; Bikulcius, G.; Gudaviciute, L.; Juzeliunas, E., Electrochem. Comm.,
2002, 4, 86.
[20] Ma, Y. P.; Wikswo, J. P.; Samuleviciene, M.; Leinartas, K.; Juzeliunas, E., J.
phys. Chem. B., 2002, 106, 12549.
[21] Rousan, A. A.; Al-Rawashdeh, N.A.F., Corrosion Engineering, Science and
Technology, 2006, 41, 235-239.

188
[22] Schramm, K. W.; Wu, W. Z.; Henkelmann, B.; Merk, M.; Xu, Y.; Zhang, Y. Y.;
Kettrup, A., Chemosphere, 1995, 31, 3445.
[23] Ghabashy, M. E.; Sedahmed, G. H.; Mansour, I. A. S., Br. Corros. J., 1982, 17, 36.
[24] Sanyel, B.; Srisvastava, K., Br. Corros. J. 1973, 8, 28.
[25] Tedesschi, R. J., Corros., 1975, 31, 130.
[26] Langmuir, L., J. Am. Chem. Soc., 1916, 38, 2221.
[27] Fouda, A. S.; Moussa, M. N. H.; Taha, F. I.; Elneenaa, A. I., Corros. Sci., 1986, 26, 719.
[28] Rucinskiene, A.; Bikulcius, G.; Gudaviciute, L; Juzeliunas, E., Electrochem. Comm.,
2002, 4, 86.

189