Corrosion Science 42 (2000) 243±257

Secondary amines as copper corrosion

inhibitors in acid media
E. StupnisÆ ek-Lisac*, A. Brnada, A.D. Mance
Faculty of Chemical Engineering and Technology, University of Zagreb, Zagreb, Croatia
Received 25 June 1998; accepted 21 April 1999

Abstract

The objective of this paper is to provide an additional insight into the study of secondary
amines as acid-corrosion inhibitors for copper. The homologous series of aromatic
secondary amines with various substituents have been investigated.
The results of the electrochemical and gravimetric measurements on copper in
hydrochloric and sulphuric acid have shown that the nonsubstituted secondary amine (N-
(2-furfuryl)-p-toluidine) has the least-e€ective inhibiting properties. The introduction of
substituents (-Cl, -Br, -NO2, -CH3) in the 5-position of N-(2-furfuryl-p-toluidine) increased
the degree of copper protection in acid media.
The comparison of results obtained in hydrochloric acid with those related to sulphuric
acid point to the activity of electrolyte anions. # 2000 Elsevier Science Ltd. All rights
reserved.

Keywords: Copper (A); Potentiostatic polarization (B); Acid inhibition (C)

1. Introduction

The interfacial behaviour of organic compounds can be modulated by

modifying substituents and functional groups. Molecules that are otherwise only

* Corresponding author. Tel.: +385-1-4597-117; fax: +385-1-4597-139.

E-mail address: ema.lisac@public.srce.hr (E. StupnisÆ ek-Lisac).

0010-938X/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 9 9 ) 0 0 0 6 5 - 7
244 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257

physically attached to the metal surface can be changed into chemically adsorbed
entities. This is of particular signi®cance in the ®eld of corrosion inhibitors.
The correlation between the inhibitor eciency and the molecular structure
(substituents and functional groups) of organic compounds has been extensively
investigated [1±7].
The amines are an interesting group of nitrogen containing organic compounds

Fig. 1. Investigated secondary aromatic amines.

 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257 245

which act as inhibitors in the dissolution of metals in aggressive media by

adsorbing at the metal-solution interface. They have been studied as corrosion
inhibitors for various metals in several media [7±17]. Although many amine
inhibitors have been studied so far, no detailed studies of the homologous series
of aromatic amines can be found in the literature.
Our recent study of the eciency of secondary and tertiary aromatic amines as
copper corrosion inhibitors in hydrochloric and sulphuric acid has shown that
secondary amines present better inhibiting properties than tertiary ones [18,19].
The aim of this paper is to study the in¯uence of various substituents on the
copper corrosion inhibition of the homologous series of aromatic secondary
amines.

Fig. 2. Potentiostatic polarization curves for copper in 0.5 M HCl () and with the addition of 0.005 M
(q) and 0.01 M (r) N-(5-methyl-2-furfuryl)-p-toluidine.
246 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257

2. Experimental procedure

Investigation of the inhibiting properties of homologous series of secondary

aromatic amines was performed by electrochemical methods using potentiostatic
polarization and gravimetric method. The experiments were carried out using
99.94% Cu as the electrode material. Electrodes were made of cylindrical copper
rods insulated with a polytetra¯uoroethylene (PTFE) band leaving only a circular
cross section (0.785 cm2) exposed. The electrode surface was abraded with emery
paper to a 1000-metallographic ®nish, polished with Al2O3 (0.3 and 0.05 mm) and
degreased with ethanol.
Measurements were made in a conventional electrolytic cell with a platinum
counter electrode using a saturated calomel electrode (SCE) as reference electrode.

Fig. 3. Anodic and cathodic Tafel lines for copper in uninhibited 0.5 M HCl () and with the addition
of 0.005 M (q) and 0.01 M (r) N-(5-methyl-2-furfuryl)-p-toluidine.
 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257 247

All reported potentials refer to SCE. The electrodes were immersed in the
solutions consisting of 0.5 M hydrochloric acid or 0.5 M sulphuric acid with
organic inhibitors at concentrations of 5  10ÿ3 M, 10ÿ2 M and 5  10ÿ2 M. The
secondary aromatic amines investigated as corrosion inhibitors in hydrochloric
and in sulphuric acid are presented in Fig. 1. All secondary amines were prepared
by sodium borohydride reduction of corresponding azomethynes according to
reported procedure [20±22].
Kinetic data were obtained directly from steady state polarization analysed on
the basis of the Tafel extrapolation and on the `linear' polarization measurement
of polarization resistance according to the procedures described elsewhere [23].
The measurements were conducted by stirring under aerated conditions at room
temperature

Fig. 4. The determination of polarization resistance for copper in 0.5 MHCl () and with the addition
of N-(2-furfuryl)-p-toluidine (w), N-(5-chloro-2-furfuryl) -p-toluidine (q); N-(5-nitro-2-furfuryl)-p-
toluidine (r) and N-(5-methyl-2-furfuryl)-p-toluidine (x) in concentration of 0.01 M.
248 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257

3. Results

3.1. Cu-O.5 M hydrochloric acid

Fig. 2 shows overall current density Ð potential potentiostatic polarization

curves of copper in 0.5 M hydrochloric acid with and without the addition of N-
(5-methyl-2-furfuryl)-p-toluidine di€erent concentrations (0.005 M and 0.01 M).
The in¯uence of the addition of N-(5-methyl-2-furfuryl)-p-toluidine on Tafel plots
is presented on Fig. 3. The determination of polarization resistance for copper in
hydrochloric acid and with the addition of investigated organic compounds is
shown in Fig. 4. Table 1. shows corrosion parameters and protecting degrees for
copper in hydrochloric acid with and without the addition of the investigated
secondary amines obtained by Tafel extrapolation method.
Results obtained by gravimetric measurements of in¯uence exerted by di€erent
inhibitors on copper corrosion in hydrochloric acid are presented in Fig. 5.
Fig. 6. shows comparative inhibiting-eciency data for investigated inhibitors as
obtained by di€erent methods (Tafel extrapolation method, polarisation resistance
measurements and gravimetric method) for copper in hydrochloric acid.

3.2. Cu-0.5 M sulphuric acid

Potentiostatic polarization curves for copper in 0.5 M sulphuric acid with and
without the addition of N-(5-chloro-2-furfuryl)-p-toluidine in di€erent
concentrations (0.01 M and 0.05 M) are presented in Fig. 7. The in¯uence of the
addition of N-(5-nitro-2-furfuryl)-p-toluidine in sulphuric acid on the anodic and
cathodic Tafel lines for copper are presented in Fig. 8. The values of the kinetic
parameters for copper in sulphuric acid with and without the addition of
investigated inhibitors, obtained by Tafel extrapolation method, are presented in
Table 2.

Table 1
Corrosion parameters and protecting degrees for copper in hydrochloric acid without and with the ad-
dition of investigated secondary amines obtained by Tafel extrapolation methoda

INHIBITOR Ecorr/mV jcorr/mAcmÿ2 ba/mV bc/mV z%

0.5 M HCI ÿ230 0.050 60 ÿ230 ±

Inhibitor 1 ÿ225 0.032 60 ÿ275 36
Inhibitor 2 ÿ105 0.011 42 ÿ60 78
Inhibitor 3 ÿ48 0.019 60 ÿ118 62
Inhibitor 4 ÿ70 0.008 15 ÿ53 84
Inhibitor 5 ÿ10 0.007 25 ÿ70 86

a
Inhibitor 1: N-2-furfuryl-p-toluidine; Inhibitor 2: N-5-chloro-2-furfuryl-p-toluidine; Inhibitor 3: N-5-
bromo-2-furfuryl-p-toluidine; Inhibitor 4: N-5-nitro-2-furfuryl-p-toluidine; Inhibitor 5: N-5-methyl-2-
furfuryl-p-toluidine.
 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257 249

Fig. 5. Weight loss of copper in 0.5 HCl (1) and with the addition of N-(2-furfuryl)-p-toluidine (2), N-
(5-chloro-2-furfuryl)-p-toluidine (3), N-(5-nitro-2-furfuryl)-p-toluidine (4) and N-(5-methyl-2-furfuryl)-p-
toluidine (5).

Fig. 6. The comparison of the inhibiting eciency data for investigated inhibitors: N-(2-furfuryl)-p-
toluidine (1); N-(5-chloro-2-furfuryl)-p-toluidine (2); N-(5-bromo-2-furfuryl)-p-toluidine (3); N-(5-nitro-
2-furfuryl)-p-toluidine (4); and N-(5-methyl-2-furfuryl)-p-toluidine (5) obtained by Tafel extrapolation
method, polarization resistance measurements and gravimetric method for copper in 0.5 HCl.
250 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257

Fig. 7. Potentiostatic polarization curves for copper in uninhibited 0.5 M H2SO4 () and with the
addition of 0.01 M (r) and 0.05 M (w) N-(5-chloro-2-furfuryl)-p-toluidine.

The determination of polarization resistance for copper in investigated solutions

are presented in Fig. 9.
Fig. 10 shows the weight loss Ð time dependence for copper in sulphuric acid,
with and without inhibitors.
The comparison of the inhibiting-eciency data obtained by di€erent methods
for copper in sulphuric acid are presented in Fig. 11.

4. Discussion

The ability of chemical adsorption and co-ordination to metal is a well-known

characteristic of the amino group. Although the adsorption strength depends on
 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257 251

Fig. 8. Anodic and cathodic Tafel lines for copper in uninhibited 0.5 M H2SO4 () and with the
addition of 0.01 M N-(5-nitro-2-furfuryl)-p-toluidine (r).

Table 2
Kinetic parameters for copper in sulphuric acid without and with the addition of investigated inhibitors
obtained by Tafel extrapolation methoda

INHIBITOR Ecorr/mV jcorr/mAcmÿ2 ba/mV bc/mV z%

0.5 M HCI ÿ48 0.032 63 ÿ140 ±

Inhibitor 1 15 0.047 42 ÿ220 ±
Inhibitor 2 75 0.006 36 ÿ75 81
Inhibitor 3 ÿ20 0.005 64 ÿ74 84
Inhibitor 4 90 0.022 45 ÿ90 31
Inhibitor 5 165 0.050 45 ÿ180 ±

a
Inhibitor 1: N-2-furfuryl-p-toluidine; Inhibitor 2: N-5-chloro-2-furfuryl-p-toluidine; Inhibitor 3: N-5-
bromo-2-furfuryl-p-toluidine; Inhibitor 4: N-5-nitro-2-furfuryl-p-toluidine; Inhibitor 5: N-5-methyl-2-
furfuryl-p-toluidine.
252 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257

Fig. 9. Polarization resistance determination for copper in 0.5 M H2SO4 () and with the addition of N-
(2-furfuryl)-p-toluidine (w); N-(5-chloro-2-furfuryl)-p-toluidine (q); N-(5-nitro-2-furfuryl)-p-toluidine
(r) and N-(5-methyl-2-furfuryl)-p-toluidine (x) in concentration of 0.01 M.

the electronic con®guration of metal, it can be correlated with the dipole moment
and steric factor of the ligand molecule.
The structure of the investigated amines is of interest as a corrosion inhibitor
because of the amino group itself but also because of the other part of the
molecule. The investigated amines have polar and unsaturated bonds like
heterocyclic ring with oxygen (furan) variously substituted in position 5 and
aromatic ring with methyl group in p-position (Fig. 1).
The electron density at the atom constituting the main reaction centre of
organic inhibitor a€ects the strength of the adsorption band by any mechanism. It
is of particular signi®cance for aromatic and heterocyclic compounds since for
them the electron density at the reaction centre can change considerably with
various substituents.
 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257 253

Fig. 10. Weight loss±time dependence for copper in 0.5 M H2SO4 (1) and with the addition of N-(2-
furfuryl)-p-toluidine (2), N-(5-chloro-2-furfuryl)-p-toluidine (3), N-(5-nitro-2-furfuryl)-p-toluidine (4)
and N-(5-methyl-2-furfuryl)-p-toluidine (5).

All substituents on the nitrogen ion can a€ect the electron density at the
reaction centre. When a hydrogen atom linked to a carbon in an amine molecule
is replaced by halogen or by any other electron-attaching group it tends to draw
electrondensity away from its neighbouring group and thus may lead to a decrease
in electron density on the nitrogen atom.
The result of these in¯uences is the reduction of the base strength of the amine.
Nitro group is acting in the same way with its electron-attracting e€ect.
On the contrary, halogen with its positive mesomeric e€ect (+M) donates
electron density to the system and so can therefore stabilise the cation (which
occurs as [R2NH2]+ in an acid electrolyte). The situation is quite similar with the
electron donating property of the CH3 group on the aromatic and furan rings.
The adsorption of such cations can be facilitated in the presence of halide ions
(synergistic e€ect). This corresponds well with the much better result of the 5-
methylsubstituted amine in hydrochloric acid solution than in sulphuric acid.
Consequently, halogen atoms are the species which can stabilize the
(unprotonated) amine with its electron-attracting e€ect as well as protonated
cation with a positive mesomeric e€ect. The high eciency of chloro and bromo
substituted amines can therefore be explained by: negative inductive e€ect (ÿI)
and positive mesomeric e€ect (+M) in adsorption processes.
The inhibiting propensity of secondary amines depends on the electronic
structure of the molecule. The in¯uence of the substituent on copper corrosion in
254 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257

Fig. 11. The comparison of the inhibiting eciency data for investigated inhibitors: N-(2-furfuryl)-p-
toluidine (1); N-(5-chloro-2-furfuryl)-p-toluidine (2); N-(5-bromo-2-furfuryl)-p-toluidine (3); N-(5-nitro-
2-furfuryl)-p-toluidine (4); and N-(5-methyl-2-furfuryl)-p-toluidine (5) obtained by Tafel extrapolation
method, polarization resistance measurements and gravimetric method for copper in 0.5 M H2SO4.

hydrochloric acid has been studied observing the normal corrosion rate to be
dependent upon the constant s in Hammett's equation [24]:

log jH =jR ˆ rs

where jH is corrosion current density in the presence of secondary amines without

substituent (N-2-furfuryl-p-toluidine), jR is the corrosion current density in the
presence of substituted amine, r is the reaction constant, and s is a measure of
the polar properties of the substituent (Hammett's constant). The dependence of
log jH/jR upon s for copper in hydrochloric acid is shown in Fig. 12.
It is obvious that the substitution of a hydrogen atom by either the nucleophilic
substituent -CH3 (s < 0), or by electrophilic substituents -Cl, -Br, -NO2 (s > 0)
increases the eciency of inhibition over that provided by nonsubstituted N-2-
furfuryl-p-toluidine itself, which is con®rmed by three methods of measurements
(Tafel extrapolation, polarization resistance measurements and gravimetric
method). These and similar results by other authors [25] involved in study of
di€erent systems are consistent with the increased inhibition deriving from greater
adsorption due to increasing strength of co-ordinate bonding resulting from easier
electron transfer [26].
 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257 255

Fig. 12. The dependence of log jH/jR upon Hammett's constant s for copper in hydrochloric acid. R:
CH3 (1); H (2); Cl (3); Br (4) and NO3 (5).

Unlike the eciency of investigated inhibitors in hydrochloric acid where all the
substituted secondary amines have good inhibiting characteristics, in sulphuric
acid only the halide (-Cl and -Br) substituted secondary amines show remarkable
inhibiting eciencies. Fig. 13 shows the dependence of log jH/jR upon Hammett's
constant s for copper in sulphuric acid.
The comparison of the results obtained in hydrochloric acid with the data
obtained in sulphuric acid point to the activity of electrolyte anions. The fact that
the corrosion current density for copper in sulphuric acid is lower than in
hydrochloric acid can be explained by the adsorption of SO2ÿ 4 ions at a copper
electrode at negative potentials, as detected by SERS spectroscopy [27,28]. This
explains the small cathodic current for copper in sulphuric acid.
The high inhibition e€ects of halide substituted secondary amines on copper in
sulphuric acid can also be explained by SERS investigations [27,28]. In sulphuric
acid solutions containing chloride ions, the chloride has replaced SO2- 4 as
256 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257

Fig. 13. The dependence of log jH/jR upon Hammett's constant s for copper in sulphuric acid. R: CH3
(1); H.(2); Cl (3); Br (4) and NO3(5).

predominant adsorbed species at the copper electrode. The adsorption of the

halide ion is evident over the potential range investigated (from ÿ500 mV to
ÿ200 mV vs Ag/AgCl) but is particularly marked at low negative potentials.

5. Conclusion

The results of the investigation of inhibitory eciency of various secondary

amines on copper corrosion in 0.5 M hydrochloric acid show that the smallest
inhibiting eciency has N-2-furfuryl-p-toluidine. The substitution of a hydrogen
atom by either the nucleophilic substituent -CH3 (s < 0), or by the electrophilic
substituents -Cl, -Br, -NO2 (s > 0) increases the eciency of inhibition over that
provided by nonsubstituted N-2-furfuryl-p-toluidine itself.
In distinction of the eciency of investigated inhibitors in hydrochloric acid
where all the substituted secondary amines have good inhibiting characteristics, in
sulphuric acid only halide (-Cl and -Br) substituted secondary amines show
remarkable inhibiting eciencies, that point at the activity of electrolyte anions.
 E. StupnisÆek-Lisac et al. / Corrosion Science 42 (2000) 243±257 257

Acknowledgements

This work is supported by the Ministry of Science and Technology of the

Republic of Croatia through Project 125012.

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