Elecrrochimico Ada, Vol. 42, No. 3, pp.

45459, 1997
Copyright 0 1996 Elsevier Science Ltd.
Printed in &eat Britain. All tights reserved
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Adsorption and inhibitive properties of four

primary aliphatic amines on mild steel in 2 M
hydrochloric acid
J. de Damborenea, J. M. Bastidas and A. J. Vhzquez

Centro National de Investigaciones Metallrgicas, CSIC, Avda. Gregorio de1 Amo 8, 28040 Madrid,
Spain

(Received 24 June 1996)

Abstract-Four n-alkyl amines (6, 8, 10 and 12 carbon atoms) were investigated as corrosion inhibitors for
mild steel in 2 M hydrochloric acid solution using gravimetric and polarization techniques. The influences of
temperature (278-308 K) and inhibitor concentration (10-1-10-6 M) were studied. Protection efficiency
improved when the inhibitor concentration and the length of the alkyl chain were increased. The four amines
tested were adsorbed on the mild steel surface according to a Frumkin isotherm. Copyright 0 1996 Elsevier
Science Ltd

Key words: n-Alkyl amine, corrosion inhibitor, mild steel, 2 M hydrochloric acid, isotherm adsorption.

1. INTRODUCTION 0.21 Mn; 0.05 Si; balance Fe. The specimens were
mechanically polished with different grades of emery
Amines are well known as corrosion inhibitors for
paper (down to 600), degreased with acetone and
iron and its alloys. The relatively high water solubility
dried. Hydrochloric acid (2 M) was used as the
of low molecular weight amines is an advantage for
corrosion test electrolyte.
their use as corrosion inhibitors [l, 21. The presence
Four primary aliphatic amines were used as
of a heteroatom in an organic compound with
corrosion inhibitors, Merck AR grades, hexyl-l-
unsaturated bonds causes an adsorption process on
amine C6HI~N (HXM), octyl-l-amine CsHlgN
the metal surface which reduces metal dissolution [3].
(OTM), decyl-l-amine C,oHl,N (DCM) and dodecyl-
In spite of the widespread use of amines as corrosion
l-amine CIZH~~N (DDM), in the lo-‘-10W6M
inhibitors, the inhibition mechanism remains unex-
concentration range.
plained.
Four temperatures, 278, 288, 298 and 308 K, were
In general, an increase in temperature, in the case
studied.
of physisorption, reduces an inhibitor’s efficiency due
Two classic techniques, gravimetric and polariz-
to its desorption from the metal surface. Thus,
ation resistance, were used, by means of which the
finding an inhibitor with high efficiency at low and
inhibitive properties of primary aliphatic amines on
high temperatures is of substantial economic
mild steel can be explained.
significance [4, 51.
Gravimetric measurements were carried out in
Corrosion inhibition efficiency increases with the
triplicate after 8, 24,48, 72 and 96 h experimentation
number of carbon atoms in the alkyl chain of the
time, and up to 50 h for the highest temperature
amine [3].
tested, using a Mettler AJ150 analytical balance,
The aim of this paper is to study the influences of
precision i 0.1 mg.
temperature and inhibitor concentration on the
Electrochemical polarization resistance (&) was
corrosion rate and inhibition mechanism of four
measured using an AMEL Model 551 potentiostat
primary aliphatic amines containing between 6 and
connected to an AMEL Model 567 function
12 carbon atoms in aqueous 2 M hydrochloric acid
generator in a three-electrode configuration. The R,
solutions using mild steel as the working electrode.
was started at rest potential, EC,,, up to +20 mV.
The experimentation time was as in the gravimetric
2. EXPERIMENTAL CONDITIONS
tests.
The mild steel used had the following chemical The specimens had a surface area of 10cm2 for
composition (wt%): 0.08 C; <0.02 P; CO.02 S; both gravimetric and electrochemical tests.

455
456 J. de Damborenea et al.

Percentage inhibitor efficiency (P) is given by

0 HEXYLAMINE IHXM)
P = [(CR - C&)/CR] x 100, where CR is the cor-
A OCTYLAMINE (OTM)
rosion rate in uninhibited solution and CR,, is the
q DECYLAMINE (OCM)
corrosion rate in inhibited solution. X DODECYLAMINE (DDM)

3. RESULTS AND DISCUSSION

2
.
3.1. Influence of temperature
Figure 1 depicts a representative example of the Rp
results for the four amines studied. For mild steel in w
2 M hydrochloric acid solution in the presence of 3
DDM, the variation in the reciprocal of R, is ii 70 -
IA.
multiplied by a factor of 1000 against the w

experimentation time at temperatures of 278 and

308 K. With small inhibitor concentrations and up to
a
0
/‘o-5-‘o-‘H
C 50
O\
m
I 10-5-ld4M
_i y+
2 lo-‘- lD-‘hl
DODECYLAMINE (DDM) \

30 - 3 \
0

/
1o+- 1d5M

10 I \ !
I I 1 ,

279 289 298 308

TEMPERATURE, OK

Fig. 2. Variation in inhibitor efficiencyagainst temperature.

20 h experimentation a great increase in the 1000/R,

parameter may be seen. This parameter is directly
related to corrosion rate.
Figure 1 also shows that corrosion increased as the
temperature increased. This effect can be clearly seen
in the case of a low concentration DDM added to the
acid solution, where the corrosion increased over the
range of temperatures tested (278-308 K) by at least
an order of magnitude.
Figure 2 shows the dependence of inhibitor
efficiency on temperature when different amounts of
amines are added. In general, inhibitor efficiency
decreased as the temperature increased, this influence
being particularly intense at low inhibitor concen-
trations. The four amines tested proved to be highly
efficient when high concentrations were added.
Furthermore, when the number of carbon atoms
contained in the chain increased, high efficiency was
obtained with more dilute solutions.
The dependence of corrosion rate on temperature
can be expressed by the Arrhenius equation:
k = A[exp(-E,/RT)]; where k is the reaction rate
40 constant, A a constant, Ea the activation energy of the
TIME, h mild steel dissolution reaction, T the absolute
Fig. I. Variation in polarization resistance, 1000/Rp, against temperature, and R the universal gas constant.
experimental time for mild steel in 2 M hydrochloric acid Figure 3 depicts an Arrhenius plot, the corrosion
inhibited with DDM. rate against the reciprocal of temperature (l/T) for
 n-Alkyl amines as corrosion inhibitors for mild steel 457

Table 2.
Corrosion rate constant, kr and kz, values obtained as a
function of the covered metal surface
@ 5x10-'M
0 16' M Correlation
aI lo-rM Temperature kl k2 coefficient
278 K 3.16 x IO-’ 1.59 x IO-9 0.999
288 K 1.48 x lO-6 1.30 x 10-r 0.997
298 K 2.30 x lO-6 4.86 x lo-* 0.944
308 K 5.41 x IO-6 1.97 x IO-’ 0.999

authors suggested that the corrosion rate, - d(Fe)/dt,

can be expressed by the sum of two rates:
-d(Fe)/dt = kr( 1 - 0) + k$3 where k, and kz are the
rate constants for the uninhibited reaction and
completely covered surface, respectively, and 8 is the
fraction of the surface covered by adsorbed inhibitor.
To confirm this hypothesis, the ratio between
1o-81 corrosion rate and surface coverage was plotted
3.24 3.35 3.L7 3.59 against the ratio (1 - 0)/O for each temperature tested
,03p 0K-1 and for each of the four amines tested. The slopes of
,
Fig. 3. Variation in mild steel corrosion rate against l/T the straight lines yielded give the values of kl and the
(Arrhenius plot) in 2 M HCl inhibited with HXM. ordinate intercepts give the values of k2. Table 2
summarizes the k, and k? values, which were fitted
with a computer programme. The corrosion rate of
mild steel immersed in 2 M hydrochloric acid in the uninhibited mild steel, 0.8 x lo-‘-5.5 x 10e6 kg mm2
presence of different HXM concentrations. The four s-l, determined using the weight loss method, agrees
amines studied showed similar behavior. The plots with the results obtained for k, and the hypothesis is
obtained are straight lines and the slope of each satisfied.
straight line gives its activation energy: The inhibition mechanism can be explained by the
E, = - 1.9 x low2 d(logk)/d(l/T) kJ mol-I. Fe(Inh),d, reaction intermediates [8]: Fe + InhoFe-
Table 1 summarizes E, values for the four amines (Inh)ads+Fe” + + ne- + Inh. At first, when there is
tested. The negative values of E, indicate the not enough Fe(Inh),,,, to cover the metal surface,
adsorption of organic compounds on the electrode because the inhibitor concentration is low or because
surface. Thus, the increase in E, could be interpreted the adsorption rate is slow, metal dissolution takes
as the physical adsorption which occurs in the first place in sites on the mild steel surface free of
stage [2]. It can be seen that for a wide range of Fe(Inh),d,. With high inhibitor concentration a
inhibitor concentrations, E, is higher in the presence compact and coherent inhibitor overlayer is formed
of inhibitor (75-90 kJ mol-I) than in the absence of on the mild steel which reduces chemical attacks on
inhibitor (70 kJ mol-I). A drop in E, was found with the metal.
the highest inhibitor concentrations studied. These
data agree with that reported in the literature [6,7].
Riggs and Hurd [4] proposed a mechanism which 3.2. Influence of amine concentration
can be applied to explain the present results. The Figure 4 shows the variation in the corrosion rate
of mild steel in 2 M hydrochloric acid solution with
inhibitor concentration at 278 and 308 K. It can be
Table 1. observed that the mild steel corrosion rate decreases
Activation energy E. (kJ mol-I) of the mild steel corrosion as the inhibitor concentration increases. At the
rate in presence and absence of inhibitor highest temperature tested (308 K) after a maximum
Concentration E, value in the corrosion rate a drop is produced.
Inhibitor (M) (kJ mol-‘) The inhibition mechanism of the n-alkyl amine
Uninhibited 2 70 may also be interpreted as the adsorption of the
hexyl- 1-amine 10-4-10-i 80-90 amine on an exposed metal atom through the
(HXM) 5 x IO-’ 29 nitrogen atom of the amine, thus forming an
octyl-l-amine 10-r-10-2 75-80 adsorption layer which acts as a hindrance to the
@TM) 5 x IO-2 35 solution and enhances the protection of the metal
decyl- 1-amine lo-r-lo-’ 75-80 surface [4].
(DCM) 10-1 50 In order to study the relationship between inhibitor
dodecyl- l-amine 10-e-5 x 10-r 85-90 adsorption on the mild steel surface and the amine
(DDM) 10-d 35
concentration (isotherm plot), the degree of surface
458 J. de Damborenea et al.

coverage, 8, was plotted as a function of the CONCENTRATION RELATIVE I V = C/Ce,,,6)

concentration of the four amines tested in the

solution (Fig. 5, solid line). 0 was calculated from the
inhibitor efficiency relationship: (CR - CRo)/CR.
Three regions can be observed on the isotherm plot:
(i) an increase in the inhibitor concentration does not
produce an increase in 8; (ii) a small increase in the
inhibitor concentration causes high 8 (a linear
dependence of 8 OSlog c); and (iii) 0 is independent
of the inhibitor concentration.
The Frumkin isotherm taken from Damaskin et al.
[9] is written as: 0 HXM
6 OTM
Kc = [0/( 1 - 0)] [exp( - 2aB)] “.A
0 DCM
I- - X DDM
where a is the interaction parameter, K is the
equilibrium constant of the adsorption reaction: -6 -5 -4 -3 -2 -1
J 0
K = (1/55S)[exp( -AG&/RQ]. The value 55.5 is the log INHIBITOR CONCENTRATION
concentration of water in the solution in mol 1-l [lo], Fig. 5. Variation in mild steel surface coverage against
AC:,, is the adsorption energy, c is the inhibitor logarithm of inhibitor concentration (isotherm plot, solid
concentration and the others have the meanings line) and relative concentration (y = C/CO
= 0.5,dotted line) in
previously defined. 2 M HCI at 288 K.

Using relative concentrations the Frumkin

O.‘~
0.5
0 HEXVLAMINE (HXM)
isotherm equation adopts the form [9]:

y = c/c6 = 0.5= [Cl/(1 - B)]{exp[a( 1 - 2611).

A OCTVLAMINE (OTM) Figure 5 (dotted line) shows the variation in surface

0 DECVLAMINE (DCM) coverage, 8, against the relative concentration,
X DODECVLAMINE(OOM) y = c/co _ 0.5.As proposed by Damaskin et al. [9], the
i
attraction constant, u, deduced from the latter
equation is: a = [2.3/(1 - 28)]1og(y(l - 0)/e]. The
attraction constant was determined as the arithmetic
mean value for each dotted line in Fig. 5. The values
obtained were in the range from 0.46 to 1.85 from the
lowest to the highest carbon atom contents in the
alkyl chain of amines, respectively.
The positive sign of the constant a, indicating
highly attractive lateral interaction forces between the
adsorbed molecules [l 11, and the sigmoidal shape of
the adsorption isotherm (Fig. 5 solid line), confirm
the applicability of Frumkin’s equation to describe
the adsorption process of the four amines tested in
2 M hydrochloric acid solution on a mild steel
electrode [lo, 12-15).
A second inhibition mechanism may also inter-
vene, consisting of adsorption through the formation
of a hydrogen bond between the protonated amine
and the metal surface [ 161. The adsorption energy of
water molecules on mild steel is very high [9]. Thus,
the first effect of an organic compound inhibitor is to
replace a water molecule with a molecule of organic
adsorbate. Frumkin’s equation does not take into
account the number of water molecules displaced. In
a second step the free amine can bond to the metal
surface. This means that if the amount of amine in the
INHlelTOR CONCENTRATION,M solution is low, the mild steel corrosion rate may
Fig. 4. Variation in mild steel corrosion rate against increase due to the possible formation of intermediate
inhibitor concentration at 288 and 298 K. products which reduce inhibitor efficiency.
 n-Alkyl amines as corrosion inhibitors for mild steel
276 OK
0 HEXYLAMINE (HXM)
A OCTYLAMINE(OTM)
0 OECYCLAMINEIOCM)
x OOOECYCLAMINE (ODMl
-6 -5 -4
log INHIBITOR CONCENTRATION
Fig. 6. Variation in logarithm of mild steel corrosion rate
against logarithm of inhibitor concentration in 2 M HCl at
288 K.
3.3. Influence of carbon atoms in alkyl amine chain
lengths
Figure 6 shows a representative example, for the
four temperatures tested, of the variation in the
logarithm of the corrosion rate for mild steel in 2 M
hydrochloric acid solution against the logarithm of
the inhibitor concentration at 278 K. It may be seen
that below a certain inhibitor concentration, referred
to as the characteristic concentration cc (which
depends on the testing temperature), the corrosion
rate remains constant.
On the other hand, the corrosion rate shows a clear
“roll-off’ at inhibitor concentrations above cc. Here
the inhibitor efficiency was higher than 90%. This
inhibition efficiency and the c, were achieved at lower
inhibitor concentrations when the length of the
aliphatic amine chains was greater (Fig. 6).
In a short molecule, such as HXM, the electron
density in the functional group on the hydrocarbon
chain may be displaced by an induction effect.
However, in amines with 8, 10 or 12 carbon atoms
this effect is unlikely [lo]. This hypothesis is
corroborated by the basicity constant theory [17].
Thus, the relative forces of an amino-group RNHr in
acid solutions (RNHg + H +oRNH: ) can be defined
according to the equilibrium constant of this
protonation process, Kb, by the relationship:
Kb = [RNH:]/[RNHz] [H+ 1. Nevertheless, the pKb
values of the four amines tested are similar in the
range of 3.44-3.37. These results may describe a steric
hindrance by which the inhibitive properties of the
amine depend on the ability to reach the metal
surface and to form a bond. However, as has been
pointed out above, inhibition may be attributed to an
adsorption effect which is more dominant than steric
hindrance. A mild steel-adsorbed compound system
459
is obtained where the former physical adsorption
process turns to chemisorption [2]. The orientation of
the compounds on the metal surface is unknown and
vertical and flat adsorbed orientations have been
proposed [18]. Finally, the positive sign of parameter
a contributes to the vertical adsorption of organic
molecules with alkyl chains protruding into the
solution [2, 151.
4. CONCLUSIONS
The corrosion rate increased by at least an order of
magnitude in the range of temperatures tested,
278-308 K. This effect is of particular significance at
-3 -2 -1
low inhibitor concentrations.
An increase in inhibitor efficiency was observed, as
a function of the inhibitor concentration, up to a
maximum value and followed by a drop.
The influence of the organic molecule chain length
from 6 to 12 carbon atoms was shown by an increase
in inhibition efficiency.
The four primary aliphatic amines tested were
chemically adsorbed on the mild steel surface
according to a Frumkin isotherm, preceded at low
concentrations by physical adsorption.
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