AC and DC study of the temperature eect

on mild steel corrosion in acid media in

the presence of benzimidazole derivatives
A. Popova
*
, E. Sokolova, S. Raicheva, M. Christov
Department of Physical Chemistry, University of Chemical Technology and Metallurgy,
8 Kl. Ohridski St, 1756 Soa, Bulgaria
Received 13 February 2001; accepted 1 March 2002
Abstract
The eect of benzimidazole derivatives on mild steel corrosion in 1 M HCl at ve dierent
temperatures has been studied. Impedance, polarization resistance, polarization curves mea-
surement and gravimetric methods have been used. The inhibiting eciency and the apparent
activation energy (E
a
) have been calculated in the presence and in the absence of the organic
inhibitors.
The comparative investigations carried out in 1 M H
2
SO
4
and 1 M H
2
SO
4
1 10
4
M KI
verify the assumption that the halogen ions facilitate the inhibitors adsorption. The electro-
static absorption of the compound cation form seems more probable. The behaviour of 2-
mercaptobenzimidazole (2-SH-BI) contrasts that of the rest of the substances investigated.
Chemisorptive adsorption is more probable in this case. The lower value of activation energy
E
a
in the presence of 1-benzyl-benzimidazole when compared to that in 1 M HCl is explained
with a partial compensation eect.
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Acidic media; Corrosion; Electrochemical impedance spectroscopy; Inhibitors; Temperature eect
1. Introduction
Temperature has a great eect on the rate of metal electrochemical corrosion. In
case of corrosion in a neutral solution (oxygen depolarization) the increase of
www.elsevier.com/locate/corsci
Corrosion Science 45 (2003) 3358
*
Corresponding author. Tel.: +359-2-622-872; fax: +359-2-685-488.
E-mail address: ck@uctm.edu (A. Popova).
0010-938X/03/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S0010- 938X( 02) 00072- 0
temperature has a favourable eect on the overpotential of oxygen depolarization
and the rate of oxygen diusion but it leads to a decrease of oxygen solubility. In case
of corrosion in an acid medium (hydrogen depolarization), the corrosion rate in-
creases exponentially with temperature increase because the hydrogen evolution
overpotential decreases. An experimental dependence of Arrhenius type is observed
between the corrosion rate and temperature:
j
corr
= k exp(E
a
=RT) (1)
where E
a
is the eective activation energy of the corrosion process in kJ mol
1
,
Rthe molar gas constant in J mol
1
K
1
, Tthe absolute temperature in K,
kthe preexponential factor and j
corr
the corrosion current density, Acm
2
.
It provides the determination of the eective activation energy of the corrosion
process.
Temperatures eects on acidic corrosion, most often in hydrochloric and sul-
phuric acid have been the object of a large number of investigations [113,17]. In
hydrochloric acid, the eective energies of activation of the corrosion process vary
in the range of 57.787.8 kJ mol
1
while most are grouped around 60.7 kJ mol
1
. In
some cases investigations are carried out at only three temperature values, using a
single experimental method which increases the probability of an incorrect deter-
mination of the corrosion activation energy. In this respect, further study is desirable
because it might oer a reliable comparative basis for discussing the results obtained.
It is generally assumed that in acid corrosion the inhibitors adsorb on the metal
surface which results in a structural change of the double layer and reduced rate of
the electrochemical partial reaction.
Temperature dependence of the inhibitor eciency (IE) and the comparison of the
values of eective activation energy (E
a
) of the corrosion process both in the absence
and in the presence of inhibitors leads to some conclusions concerning the mecha-
nism of the inhibiting action. Temperature increase leads to a decrease in IE, with the
resulting variation of the eective activation energy value (the latter is in general
higher than that in the inhibitors absence) often interpreted as an indication of the
formation of an adsorptive lm of a physical (electrostatic) character. The opposite
dependence (lower activation energy in an inhibited solution) demonstrates that a
chemisorptive bond between the organic molecules and the metal surface is probable
[4,7,9,1416].
Acid picking of steel is usually carried out at elevated temperaturesup to 60 C
in hydrochloric and up to 90 Cin sulphuric acid. The inhibitors used are expected
to be chemically stable to provide high protective eciency under the conditions
mentioned above. This is relevant to the practical aspects of the present investiga-
tion.
We report the results of an experimental study of the eect of temperature on mild
steel corrosion process in 1 M HCl both in the absence and in the presence of a
selected series of inhibitors (Table 1) which are derivatives of benzimidazole (BI).
The choice of the compounds is based on molecular structure considerationsthe
presence of amino-, mercapto-groups and aromatic rings is likely to facilitate the
34 A. Popova et al. / Corrosion Science 45 (2003) 3358
adsorption of the compounds on the metal surface. The molecules of 2-NH
2
-BI and
2-SH-BI are of a similar volume, which provides a comparison of the eect of two
dierent functional groups. The introduction of one or two benzyl groups changes
essentially the volume of the molecule and hence the surface occupied when ad-
sorbing at the metal.
The eect of temperature on the values of the electrochemical parameters char-
acterizing the systems has been recorded by three electrochemical methods: the
impedance method, polarization resistance and of polarization curves.
An attempt was made to elucidate the dominant active form of the compounds
(molecular and/or ionic) during the adsorption process in hydrochloric acid, taking
into consideration their behaviour observed in sulphuric acid.
2. Experimental
The experiments were carried out using a standard electrochemical three-electrode
cell. A mild steel cylinder pressed into a Teon holder acted as a working electrode
Table 1
Benzimidazole derivatives
Compound Abreviation Structural formula Molar mass
1. Benzimidazole BI 118.14
2. 2-Aminobenzimidazole 2-NH
2
-BI 133.09
3. 2-Mercaptobenzimidazole 2-SH-BI 150.20
4. 1-Benzylbenzimidazole 1-BBI 208.12
5. 1,2-Dibenzylbenzimidazole 1,2-DBBI 298.20
A. Popova et al. / Corrosion Science 45 (2003) 3358 35
(WE). Its working area of 0.5 cm
2
remained precisely xed. A saturated calomel
electrode (SCE) connected through a salt bridge was used as reference electrode,
while a large area platinum leaf was used as counter electrode.
Prior to each experiment the WE was wet polished with 600 grade emery paper,
rinsed with distilled water and an ethanolether mixture and then immediately in-
serted into the glass cell, that contained 250 ml of electrolyte solution. The latter was
deaerated by argon for 1 h prior to the insertion of the WE and for 1 h after. The
eect of the exposure duration in 1 M HCl on the impedance spectrum (IS) was
studied as in Ref. [18]. The results obtained provided the determination of the WE
exposure time. It was found that 1 h exposure was suitable in case of high temper-
atures. the same exposure time was adopted before applying polarization resistance
and polarization curves method as well. This was required by the comparative ex-
amination envisaged. Hence, all electrochemical experiments were carried out after
1 h of exposure to the solution.
EG&G Instruments electronic equipment was used. It included a PAR Model 273
Potentiostat and a 5208 Two Phase Lock-in Analyzer which enabled impedance
measurements from 100 lHz to 100 kHz. They were monitored by an IBM-AT
personal computer via a GPIB-IIA Interface. Two programmes, M378 and M342
were used for collecting and evaluating the experimental data.
The data obtained by the three experimental methods were compared.
Our investigation measured the response of the electrochemical system to AC
excitation with a frequency ranging from 95 kHz to 0.1 Hz and peak to peak AC
amplitude of 5 mV. The lock-in amplier technique was used for the frequency range
of 5 Hz to 95 kHz with 5 points per decade. Measurements below 10 Hz were made
using the fast Fourie transformation (FFT) technique with eight data cycles. Various
equivalent circuit models were tted to the impedance data using a non-linear op-
timization computed programme.
When applying the polarization resistance method, the WE was polarized in the
range of 10 mV vs. E
corr
, at a scan rate of 0.1 mVs
1
. The polarization curves in the
range about 200 to 120 mV vs. E
corr
measured were recorded separately, again
with a scan rate of 0.1 mVs
1
. PARCalc 342 data analysis technique was used. It
uses a v
2
minimization technique to nd the value of the Tafel constants, corro-
sion potential and corrosion current density that best represent the experimental
data. The SternGeary equation for kinetics is used to determine the best-t value of
b
a
, b
c
, E
corr
, j
corr
and polarization resistance R
p
.
Most of the experiments were conducted at 20, 30, 40, 50 and 60 C.
All the plots and the calculated values are the means of at least three independent
measurements. The average standard deviation is reported as well.
The inhibition eciency of the compounds was studied through weight loss
measurements at the denite time interval of 24 h at room temperature (20 C 1).
In this case the working specimens were of a round shape to avoid the eects of edges
where high speed corrosion occurs, with an area of 11.3 cm
2
. They were made from
mild steel sheets. Beakers containing 250 ml solution were used. Three specimens
were immersed in each beaker. The weight of each specimen was determined prior to
and after exposure to the solution investigated.
36 A. Popova et al. / Corrosion Science 45 (2003) 3358
The inhibition eciency, IE(%), is calculated from the gravimetric data by the
formula:
IE(%) =
W
0
W
i
W
0
100 (2)
where W
0
(g m
2
h
1
) is the average corrosion rate in the absence of the inhibitor
studied and W
i
(g m
2
h
1
) is the average corrosion rate in its presence.
The inhibition eciency can be calculated on the basis of the data from the
electrochemical experiments by:
IE(%) =
j
0
corr
j
inh
corr
j
0
corr
100 (3)
where j
0
corr
and j
inh
corr
are the corrosion current density in the absence and in the
presence of an inhibitor, respectively.
The value of the protection coecient c is calculated in accordance with:
c =
j
0
corr
j
inh
corr
(4)
Electrochemical corrosion with hydrogen depolarization is characteristic for the
systems investigated. The kinetics of the process is studied in more details in Ref.
[19]. The whole surface of the samples is attacked by corrosion. As no local corrosion
is experimentally observed, the average corrosion rate (g m
2
h
1
) and the inhibitor
eciency may be calculated using the formulae given above [1,4,15,16,2023,56].
3. Results and discussion
Fig. 1 presents the dependence of the inhibition eciency IE(%), calculated from
gravimetric data, on the molar (M) concentration, c
i
of the compounds studied at
room temperature (20 C 1). The upper limit of the concentration interval is
limited by the solubility of each substance.
Fig. 1. Dependence of the inhibition eciency IE(%) on the concentration of the compounds c
i
(M) for of
mild steel corrosion in 1 M HCl: (

) BI; (
v
) 2-NH
2
-BI; ( ) 2-SH-BI; (

) 1-BBI; () 1,2-DBBI.
A. Popova et al. / Corrosion Science 45 (2003) 3358 37
The data plotted in Fig. 1 show that the inhibiting eectiveness of the compounds
investigated depends on their inhibitor concentration and on the structure of the
molecule.
Consequent investigations on temperature eects were carried out at concentra-
tions selected on the basis of the data in Fig. 1. The following values of c
i
(char-
acterized either by the highest IE(%) or by IE(%) which no longer changes) have
been chosen: 2 10
2
M for BI and 2-NH
2
-BI, 10
3
M for 2-SH-BI and 1,2-DBBI
and 5 10
3
M for 1-BBI. Inhibitors chemical adsorption on the metal surface may
be expected at high concentration values according to others [2,4], even in cases when
physical adsorption is proceeding in the lower concentration range. The validity of
this statement for the corrosion systems investigated was examined in this study.
3.1. Interface structure model in inhibitors absence and presence
The IS measurements were carried out at various temperatures in the range of 20
60 C at the open circuit potential, i.e. at the corrosion potential, E
corr
.
Let us rst consider the interface mild steel/1 M HCl. The typical IS exhibits a
single semicircle shifted along the real Z
/
axis at the investigated temperature values.
The simplest approach require the theoretical transfer function Z(x) to be rep-
resented by a parallel combination of a resistance R
1
and a capacitance C, both in
series with another resistance R
2
, i.e.
Z(x) = R
2

1
1=R
1
ixC
(5)
The resistance R
2
is identied with the ohmic resistance R
X
, which is a sum of the
electrolytic resistance and the electrical leads resistance, while C is identied with the
double layer capacitor, C
d
, i =

1
_
, x is frequency in rad s
1
, x = 2pf and f is
frequency in Hz. The high concentration of the deaerated hydrochloric acid (the low
value of pH) and the great mobility of the hydrogen ions as well as the extra stirring
of the precathodic layer, resulting from gaseous hydrogen evolution, determine the
activation control of the corrosion process. This means that the Faradaic impedance,
Z
F
which accounts in general for the proceeding of the electrochemical reaction, will
be represented by the charge transfer resistance, R
ct
. Therefore R
1
is in fact identied
by R
ct
.
The parameters calculated on the basis of the equivalent circuit oered pass in-
adequately to the impedance data and cannot explain the depression of the capac-
itance semicircle in the Nyquist plot (Z
/
in Xcm
2
Z
//
in Xcm
2
).
The classical approach to impedance modelling, based on the assumption that the
interface model should contain lumped elements only, such as R, C, L and Warburg
impedance, cannot be always applied. This type of modelling suits homogeneous
systems in which the space distribution of the parameters is lacking or is insigni-
cant. These objects which could be described by a homogeneous system of partial
dierential equations, are indicative of the electrochemical kinetics and the diusion
limitations.
38 A. Popova et al. / Corrosion Science 45 (2003) 3358
In impedance spectroscopy practice a number of experimental results show a
frequency distribution of the parameters. The latter determined the necessity of a
modelling element with frequency dispersion behaviour. The constant phase element
(CPE) which is distributed by its very nature is such an element [15,2431,69]. The
impedance of CPE is presented by:
Z
CPE
= A
1
(ix)
n
(6)
where A is a proportional factor and n has a meaning of phase shift. It is seen that at
n = 1, CPE gives pure capacitance behaviour whose impedance is:
Z
C
= (ixC)
1
(7)
Lately, many authors use CPE for modelling of frequency dispersion behaviour
corresponding to dierent physical phenomena such as surface heterogeneity which
results from surface roughness, impurities, dislocations, grain boundaries [24,25,
32,7073], fractality [2428,33], distribution of the active sites, adsorption of inhib-
itors, formation of porous layers [19,73]. In this context n can be used as a measure
of the surface inhomogeneity [19,25,28,32,74].
The corroding surface of mild steel in 1 M HCl is inhomogeneous because of its
roughness, presence of impurities, dislocations, grain and subgrain morphology, etc.
On the basis of what is stated above, the system studied here can be expected to be
characterized by distributed capacitance. The depression of the capacitance semi-
circle, whose centre lies under the real axis, conrms this as well. The distributed
capacitance is presented through CPE and the structural model of the interface mild
steel/1 M HCl is shown in Fig. 2a. Parts b and c of Fig. 2 illustrate the fact that the
parameters values calculated with the applications of the structure model in Fig. 2a
t the experimental data.
The values of the parameters determined at various temperatures on the basis of
the structure model oered are summarized in Table 2. The values of the polarization
resistance, R
DC
p
, obtained by the direct current method of polarization resistance, are
also included for comparative purposes.
It is seen that the charge transfer resistance, R
ct
, decreases with the increase of
temperature. This is connected with the corrosion rate increase.
The depression of the double layer capacitance semicircle grows as well, i.e. the
values of n
d
had a tendency to decrease. If n
d
is accepted to be measure the surface
inhomogeneity [24,25,28,32,74], then its decrease should be connected with certain
increase in heterogeneity resulting from surface metal roughening. The latter may be
caused by enhanced dissolution of the metal, which takes place at high temperatures
during exposure to the solution. The double layer capacitance C
d
is distributed and
the value of n
d
is dierent at the dierent temperatures, hence the comparison is
incorrect. Rough comparison can be done, if the values of the proportionality factor
A in s
n
X
1
cm
2
are then recalculated in s X
1
cm
2
= Fcm
2
, which is the pure
capacitance dimension. Increase of A value in (Fcm
2
) is observed with temperature
increase.
The eect of temperature on the impedance response of the system in the presence
of ve inhibitors has been studied.
A. Popova et al. / Corrosion Science 45 (2003) 3358 39
The structure model describing the interface in the presence of 2 10
2
M BI and
2 10
2
M 2-NH
2
-BI is like that in 1 M HCl without an inhibitor (Fig. 2a).
Fig. 2. Equivalent electrical circuits of the interface mild steel/1 M HCl (a) and corresponding impedance
diagrams at 50 Ccomplex plane plot (b) and Bode plot (c): (O) experimental data; ( ) calculated.
40 A. Popova et al. / Corrosion Science 45 (2003) 3358
The models parameters in presence of 2 10
2
M BI at various temperatures are
presented in Table 3. They show, when compared to those characterizing the system
with no inhibitor, that the organic compound is adsorbed on the metal surface at all
temperatures studied. The values of n
d
, like in pure acid, decrease with temperature
increase, but the dependence is better expressed. Thus, n
d
at 20, 30 and 40 C is lower
in pure acid than in the presence of 2 10
2
M BI inhibitor. This may be connected,
from an energetic point of view, with the inhibitors adsorption at the most active
sites on the metal surface and their isolation so that the surface as a whole behaves as
one of lower heterogeneity [25]. However at 50 and 60 C the values of n
d
in pure and
BI inhibited 1 M HCl coincide while the values of R
ct
in the presence of BI are
slightly greater than those for 1 M HCl. This shows that the compound has expe-
rienced a signicant decrease in its protective properties. Hence, the decrease of n
d
, in
the presence of 2 10
2
M BI may be connected with two eects: a certain drawing
of the adsorptiondesorption equilibrium towards desorption and roughening of the
metal surface which results from enhanced corrosion.
The variation of model parameters with temperature, in presence of 2 10
2
M 2-
NH
2
-BI, is analogous. However the values of R
ct
in the presence of 2-NH
2
-BI at high
temperatures are greater when compared to those in the presence of BI. This could
mean that the amino-compound has a higher protective eect.
Table 2
Interface mild steel/1 M HCl
Temperature (C)
20 30 40 50 60
R
ct
(Xcm
2
) 53.2 3.0 30.1 3.0 17.4 0.1 8.0 3.0 2.8 0.2
A
d
(Xs
n
cm
2
) 1475 220 1406 160 1105 80 612 50 275 5
10
4
A
d
(s
n
X
1
cm
2
) 6.78 7.11 9.05 16.34 36.36
10
4
A
d
(s X
1
cm
2
= Fcm
2
) 21.80 22.70 29.78 55.30 111.80
n
d
0.84 0.01 0.84 0.01 0.83 0.01 0.81 0.01 0.80 0.01
R
X
(Xcm
2
) 1.0 1.0 0.7 0.7 0.4
R
DC
p
(Xcm
2
) 53.9 2.8 30.2 3.0 17.4 0.1 8.2 1.0 3.1 0.1
Table 3
Interface mild steel/1 M HCl 2 10
2
M BI
Temperature (C)
20 30 40 50 60
R
ct
(Xcm
2
) 137:3 0:7 92.4 1.0 26.3 1.0 13.0 2.0 5.2 0.4
A
d
(Xs
n
cm
2
) 4817 215 4793 328 2088 200 1005 102 520 90
10
4
A
d
(s
n
X
1
cm
2
) 2.07 2.09 4.87 9.95 19.23
10
4
A
d
(s X
1
cm
2
= Fcm
2
)
6.25 6.83 15.07 37.00 67.17
n
d
0.87 0.01 0.86 0.01 0.85 0.02 0.81 0.01 0.80 0.01
R
X
(Xcm
2
) 0.9 0.9 0.7 0.5 0.5
R
DC
p
(Xcm
2
) 134.0 2.0 93.4 0.8 27.0 2.0 11.1 3.0 5.0 0.4
A. Popova et al. / Corrosion Science 45 (2003) 3358 41
Upon introduction of 1 10
3
M 2-SH-BI into the corrosion system, the interface
mild steel/1 M HCl 10
3
M 2-SH-BI is described by the simple equivalent circuit
presented in Fig. 2a but only at 60 C. Attempts to model the interface using the
same equivalent circuit were unsuccessful in case of temperature lower than that
mentioned above. The same is also true for the experiments conducted in presence of
5 10
3
M 1-BBI and 10
3
M 1,2-DBBI.
The transfer function of the equivalent circuit in Fig. 2a ts very well the im-
pedance data at medium and low frequencies but deviates at high frequencies.
Changes in the impedance characteristics of the interface are observed. This is ex-
pressed in the complex plane plot (Z
/
Z
//
) by the appearance of the extra capacitance
part at high frequencies (Fig. 3 shows a section of the Nyquist plot using dierent
scale) and in the Bode plot by the characteristic change of phase angle U and the
slope of log [Z[ with the frequency variation and indicates for the presence of a
second time constant. This is connected with an additional relaxation process, whose
proceeding is outlined in presence of the best inhibitors at lower temperatures, when
a higher degree of metal surface saturation by adsorbed molecules is observed.
The high frequency capacitive semicircle can be attributed to a charge transfer
process, and the neighbouring second semi circle to the inhibitors adsorption on the
metal surface [34,35].
The second structure model of the interface which has just been oered (Fig. 4a)
nicely ts the impedance data obtained at 40 and 50 C in the presence of 10
3
M 2-
SH-BI (Fig. 4b and c) as well as in the presence of 5 10
3
M 1-BBI and 10
3
M 1,2-
DBBI at all temperature values studied (Fig. 5).
The interference mild steel/1 M HCl 10
3
M 2-SH-BI is well described, at
temperatures as high as 50 C, by the structure model of Fig. 4a and at 60 Cby the
structure model presented in Fig. 2a. This shows that the ratio of the two time
constants, characterizing relaxation processes in the electrical double layer (DEL)
and in the adsorption layer, varies with temperature increase. The double layer time
constant starts to dominate at 60 C; the adsorption time constant could not be
identied. This may be explained by the increased corrosion rate at high tempera-
tures. It is interesting to note that the compound maintains very good protective
Fig. 3. High frequency range of the complex plane plot.
42 A. Popova et al. / Corrosion Science 45 (2003) 3358
properties even at 60 C. This conclusion is drawn on the basis of the R
ct
value
compared to that in 1 M HCl with no inhibitor.
Fig. 4. Structure model of the interface mild steel/1 M HCl inhibitor (a) and impedance diagrams for
mild steel in 10
3
M 2-SH-BI at 50 Ccomplex plane plot (b) and Bode plot (c): (O) experimental data;
( ) calculated.
A. Popova et al. / Corrosion Science 45 (2003) 3358 43
The calculated parameters characterizing the interfaces mild steel/1 M HCl 10
3
M 2-SH-BI and mild steel/1 M HCl 10
3
M 1,2-DBBI are presented in Tables 4
and 5, respectively. It is seen that the temperature increase leads to an essential
decrease of R
a
value which on one hand may be attributed to the corrosion rate
increase, and on the other to the probable partial desorption of the inhibitor under
these conditions. This eect is accompanied by a certain decrease in the depression of
the adsorption capacitive semicircle. It reects on the value of n
a
which is dierent
Fig. 5. Bode plot for mild steel in 10
3
M 1,2-DBBI at 50 C: (O) experimental data; ( ) calculated.
Table 4
Interface mild steel/1 M HCl 1 10
3
M 2-SH-BI
Temperature (C)
40 50 60
R
a
(Xcm
2
) 464.0 22.0 160.0 4.0
A
a
(Xs
n
cm
2
) 6051 200 9837 620
10
4
A
a
(s
n
X
1
cm
2
) 1.65 1.02
10
4
A
a
(s X
1
cm
2
= Fcm
2
) 19.76 13.34
n
a
0.72 0.01 0.72 0.01
R
ct
(Xcm
2
) 42.2 39.0 6.0 2.5 56 3.0
A
d
(Xs
n
cm
2
) 35862 1600 34631 1710 6051 200
10
6
A
d
(s X
1
cm
2
= Fcm
2
) 27.9 28.9 165
10
6
A
d
(s X
1
cm
2
= Fcm
2
) 64.5 60.0 985
n
d
0.91 0.01 0.93 0.01 0.80 0.01
R
X
(Xcm
2
) 0.6 0.5 0.4
R
DC
p
(Xcm
2
) 468.0 12.0 158.6 3.0 53.0 3.7
44 A. Popova et al. / Corrosion Science 45 (2003) 3358
for the various inhibitors and besides, varies with the temperature. Hence, the value
of n
a
might be ascribed to the energy distribution in the adsorption layer which seems
to depend on the nature of the inhibitor, i.e. on the molecular structure as well as on
the amount of the compound adsorption.
The value of R
ct
cannot be precisely determined in the presence of the three in-
hibitors studied. Most probably it is also a distributed parameter [24,2628].
The depression of the double layer capacitance semicircle n
d
does not change with
the temperature increase in the case of 1,2-DBBI and 1-BBI, but decreases slightly in
presence of 2-SH-BI.
The values of R
a
and R
ct
show that 1,2-DBBI and 1-BBI preserve high protective
properties even at high temperatures.
On the ground of the impedance investigation, the temperature eect on the
corrosion process in inhibitors presence can be summarized as follows on tem-
perature increase: (i) the rate of the corrosion proceeding on the bare surface grows
(R
ct
decreased), (ii) the adsorption/desorption equilibrium is most probably shifted
towards desorption (R
a
and A
a
in Fcm
2
decreased). But the concentration of the
inhibitor is high enough to sustain an inhibiting adsorption layer. It may be assumed
that the density of the layer of adsorbed particles within outer Helmholtz layer
(OHL) decreases while the diuse part of double electrical layer increases.
3.2. Apparent activation energy of metal dissolution process
3.2.1. Eect of temperature on the inhibition eciency
The change of the corrosion process rate with the temperature increase was
studied in 1 M HCl, both in the absence and in the presence of inhibitors.
The corrosion current density j
corr
was determined in two ways, (1) from whole
polarization curves by extrapolation of the Tafel slopes b
c
and b
a
and (2) by the
Table 5
Interface mild steel/1 M HCl 1 10
3
M 1,2-DBBI
Temperature (C)
40 50 60
R
a
(Xcm
2
) 870.4 100.0 368.4 38.2 150.5 5.1
A
a
(Xs
n
cm
2
) 9884 790 6998 247 9049 481
10
4
A
a
(s
n
X
1
cm
2
) 1.01 1.42 1.10
10
4
A
a
(s X
1
cm
2
= Fcm
2
) 57.90 53.90 14.16
n
a
0.56 0.01 0.59 0.01 0.72 0.01
R
ct
(Xcm
2
) 75:0 50:0 30.0 23.0 3.3 2.0
A
d
(Xs
n
cm
2
) 66659 3100 47764 3000 40998 4700
10
6
A
d
(s
n
X
1
cm
2
= Fcm
2
) 15.0 20.9 24.4
10
6
A
d
(s X
1
cm
2
= Fcm
2
) 40.7 55.2 63.4
n
d
0.91 0.01 0.91 0.01 0.91 0.01
R
X
(Xcm
2
) 0.5 0.5 0.4
R
DC
p
(Xcm
2
) 775.0 160.0 310.0 0.2 148.0 8.1
A. Popova et al. / Corrosion Science 45 (2003) 3358 45
R
p
-method using 324PARCalc program. These determinations are based on the data
obtained at ve temperature values.
The corrosion current density j
corr
increased with increasing temperature, by
dierent amounts in the presence of the various compounds, i.e. the nature of the
organic substances aected the electrochemical parameters.
The temperature dependence of mild steel dissolution in deaerated 1 M HCl and
in presence of the inhibitor 1-BBI is presented in Arrhenius co-ordinates in Fig. 6.
The current density values obtained by both methods are shown. The parameter j
pc
corr
stands for the current density values obtained from the polarization curves (indicated
as in Fig. 6); j
R
p
corr
was determined by the R
p
-method (indicated as in the gure).
It is important to point out that these are the mean values from three independent
experiments. The most probable line can be drawn on the basis of all data included in
the gure. Then the values of the apparent activation energy E
a
and of the preex-
ponential factor k are calculated. The correlation coecient r also is shown. The
results obtained are shown in Table 6.
The value of 61.33 kJ mol
1
obtained for the activation energy E
a
of the corrosion
process in 1 M HCl lies in the range of the most frequently cited values, the majority
of which are grouped around 60.7 kJ mol
1
[2].
The values of E
a
obtained in solutions of high inhibitor concentrations (where
one can assume that a high, even a maximum surface coverage is reached) were
greater than that of the uninhibited reaction in 1 M HCl. The only exclusion was
observed in case of 1-BBI presence.
Fig. 6. Temperature dependence of mild steel corrosion in deaerated 1 M HCl (Arrhenius plots): (a) 1 M
HCl; (b) 1 M HCl 5 10
3
M 1-BBI: () polarization curves, (

) polarization resistance, R
p
.
46 A. Popova et al. / Corrosion Science 45 (2003) 3358
Table 7 shows the change of inhibition eciency IE(%) and of the protection
coecient c (Eqs. (3) and (4)) with temperature variation. It is assumed that the
inhibitor eciency, calculated from Eqs. (2) and (3) is comparable to the fractal h of
the metal surface covered by the adsorbed inhibitors [4,15,16,56,57]. It is seen that all
compounds investigated have inhibiting properties at all temperatures studied. BI
appears to be the poorest inhibitor and its protective properties decrease by about
30% upon temperature increase. These results support the data obtained from the
impedance studies.
2-NH
2
-BI has a higher protective eect when compared to BI. Its eectiveness
preserved to a great extent when temperature is increased.
2-SH-BI, 1-BBI and 1,2-DBBI are compounds with very good inhibiting prop-
erties which change only insignicantly with temperature increase, e.g. IE(c)
decreases in presence of 2-SH-BI and 1,2-DBBI and increases slightly in presence of
1-BBI with temperature increase. In fact, 1-BBI is the compound in whose presence
the process of metal dissolution is characterized by an activation energy less than
that in the uninhibited 1 M HCl. This surprising fact has found dierent interpre-
tations in the literature.
Radovici [9] classies the inhibitors into three groups according to the tempera-
ture eects:
1. Inhibitors whose IE decreases with temperature increase. The value of the ap-
parent activation energy E
a
found is greater than that in the uninhibited solu-
tion.
Table 6
Apparent activation energy of mild steel dissolution in the presence of inhibitors
E
a
(kJ mol
1
)
Inhibitor Polarization curves R
DC
p
method Total
2 10
2
M BI 76.81 68.93 72.87
q = 0:997 q = 0:987 q = 0:989
k = 4:7 10
15
k = 2:5 10
14
k = 1:1 10
15
2 10
2
M 2-NH
2
-BI 66.55 63.75 65.15
q = 0:989 q = 0:973 q = 0:981
k = 2:6 10
13
k = 8:8 10
12
k = 1:5 10
13
1 10
3
M 2-SH-BI 78.58 70.69 74.63
q = 0:958 q = 0:977 q = 0:965
k = 8:3 10
14
k = 3:8 10
13
k = 1:8 10
14
5 10
3
1-BBI 56.81 56.57 56.69
q = 0:992 q = 0:994 q = 0:993
k = 1:1 10
11
k = 9:4 10
10
k = 1:0 10
11
1 10
3
M 1,2-DBBI 67.20 68.98 68.09
q = 0:989 q = 0:997 q = 0:992
k = 5:3 10
12
k = 9:4 10
12
k = 7:1 10
12
1 M HCl 65.94 56.73 61.33
q = 0:980 q = 0:987 q = 0:978
k = 1:3 10
14
k = 4:4 10
12
k = 2:4 10
13
A. Popova et al. / Corrosion Science 45 (2003) 3358 47
2. Inhibitors whose IE does not change with temperature variation. The apparent
activation energy does not change with the presence or absence inhibitors.
3. Inhibitors in whose presence the IE increases with temperature increase while the
value of E
a
for the corrosion process is smaller than that obtained in the uninhib-
ited solution. This is an indication, according to the author, for a specic type of
adsorption of the inhibitors.
Machu [36] also states that the corrosion process taking place in the presence of
powerful inhibitors is characterized by an activation energy whose value is smaller
than that of the uninhibited process.
The fact that IE increases with temperature is explained by [7] as the likely specic
interaction between the iron surface and the inhibitor.
The lower value of the activation energy of the process in an inhibitors presence
when compared to that in its absence is attributed to its chemisorption, while the
opposite is the case with physical adsorption [15,16].
Balezin [14] considers the increase of IE with temperature increase as the change
in the nature of adsorptionsthe inhibitor is adsorbed physically at lower tem-
peratures, while chemisorption is favoured as temperature increases.
The same phenomenon is explained by others [37] as due to increase in the surface
coverage by an inhibitor. Thus, at a high degree of coverage, the diusion through
the surface layer containing the inhibitor and corrosion products becomes the rate-
determining step of the metal dissolution process.
Let us examine the temperature behaviour of the substances investigated. Taking
into consideration the references mentioned above, we could draw the following
conclusions concerning the inhibitors adsorption.
Our experimental nature of data (those obtained at 60 C in presence of 2-SH-BI,
1-BBI and 1,2-DBBI, in particular) demonstrated that the protective eect achieved
is great. This eect can be attributed to a strong adsorption bond which, especially in
case of 1-BBI, can be interpreted [4,7,9,1416] as chemisorptive. Moreover, the in-
hibitors have been studied at high concentrations when chemisorption is expected
[2,4] to prevail. The decrease of IE value with temperature increase and the higher
value of E
a
in presence of BI and 2-NH
2
-BI can be interpreted as an indication for a
physical or coulombic type of adsorption. Hence, the explanation given in reference
Table 7
Temperature dependence of inhibitor eciency
t C 2 10
2
M
BI
2 10
2
M
2-NH
2
-BI
1 10
3
M
2-SH-BI
5 10
3
M
1-BBI
1 10
3
M
1,2-DBBI
IE(%) c IE(%) c IE(%) c IE(%) c IE(%) c
20 60.0 2.5 86.8 7.6 97.0 31.4 97.2 35.4 98.2 54.5
30 53.3 2.1 86.1 7.2 96.0 26.3 97.4 37.8 98.0 49.6
40 45.9 1.9 85.4 6.8 95.5 22.2 97.5 40.0 97.8 45.4
50 38.0 1.6 84.7 6.5 94.7 18.9 97.6 42.3 97.6 41.9
60 29.5 1.4 84.0 6.3 93.9 16.3 97.8 44.6 97.4 38.9
48 A. Popova et al. / Corrosion Science 45 (2003) 3358
[37] in regard to eciency increase with temperature, is not applicable in our case.
The reason is that the impedance investigations carried out in the presence of all
inhibitors studied, including 1-BBI, do not show Warburg impedance which usually
models diusion limited processes [38].
In general, the proceeding of physical adsorption requires the presence of both
electrically charged surface of the metal and charged species in the bulk of the so-
lution. Chemisorption process involves charge sharing or charge transfer from the
inhibitor molecules to the metal surface to form a coordinate type of a bond. This is
possible in case of a positive as well as a negative charge of the surface. The presence
of a transition metal, having vacant, low-energy electron orbital and of an inhibitor
with molecules having relatively loosely bound electrons or heteroatoms with lone-
pair electrons is necessary [33,34,41]. However the substances we studied are organic
bases which protonize in an acid medium, predominantly aecting the nitrogen atom
(N
3
) in the imidazole ring. Thus, they become cations, existing in equilibrium with
the corresponding molecular form:
In the case of an existing adsorption layer, the inhibitors eciency depends on
the forces which determine bonding with the metal surface as well as on the nature of
the interactions in the layer itself.
On the other hand, the presence of chloride ions in the solution, which are usually
characterized by strong adsorbability on the metal surface, cannot be neglected.
They should have facilitated physical adsorption of the inhibitors cations.
Obviously, the temperature investigations are indispensable but are not adequate
to elucidate the adsorption mechanism. Aiming the latter, it is necessary to establish
what is the mode of the adsorbed compoundsmolecular or ionic. Which of these
modes of adsorption predominates will depend on the molecular structure of the
compounds, on the type of the acid anions, on the position of the corrosion potential
of iron with respect to the potential of zero charge (PZC) E
q=0
. That is why the
inhibiting behaviour in HCl of the compounds studied is compared to that in H
2
SO
4
with KI as an additive.
3.2.2. Eect of the acids anion
As mentioned above, physical adsorption is the result of electrostatic attractive
forces between inhibiting organic ions or dipoles and the electrically charged surface
of the metal. The surface charge of the metal is due to the electric eld existing at the
metal/solution interface. The surface charge can be dened by the position of the
corrosion potential E
corr
in respect to the respective PZC. When the dierence
E
r
= E
corr
E
q=0
, where E
r
is the Antropovs rational corrosion potential, is
negative, the electrode surface has a negative net charge and the adsorption of ca-
tions is favoured. On the contrary, the adsorption of anions is favoured when E
r
A. Popova et al. / Corrosion Science 45 (2003) 3358 49
becomes positive [44]. The following values of PZC in H
2
SO
4
are found in the lit-
erature: 0.00 V(NHE) [43,44], 0.35 V(NHE) [45], 0.37 V(NHE) [46,49], 0.7
V(NHE) [39,47]. The rst value was calculated by Antropov on the ground of
electron-work function W
e
(E
q=0
= W
e
4:7). It was assumed that the potential drop
arising in water adsorption at the metal surface and the potential drop in the bulk of
the metal do not depend on the nature of the metal at PZC. This assumption was
found incorrect in Ref. [48] and the value of 0.370.4 V(NHE) for PZC was rec-
ommended.
Taking into consideration the stated above, the surface charge of iron in a sul-
phuric acid solution at the free corrosion potential is positive (E
corr
about 0.2
V(NHE). E
q=0
about 0.37 V(NHE) [7,15,39,59,50] or slightly less negative when
compared to that in HCl [16,42]. Hence, poor adsorption of organic cations can
occur.
Thus, a certain determination of the inhibiting properties of the compounds in-
vestigated in 0.5 M H
2
SO
4
can be expected if they act as cations and adsorb elec-
trostatically. If they adsorb chemically as molecules, their inhibiting properties are
not due to change. That is why the IE of the organic compounds studied is compared
both in 1 M HCl and H
2
SO
4
. Moreover, the concentration of H
2
SO
4
equals that of
HCl in respect to the anion.
The concentration range of the inhibitors studied in 1 M H
2
SO
4
is analogous to
that of the investigation carried out in 1 M HCl. The maximum concentration value
achieved was limited by the solubility of the corresponding compound. The gravi-
metric method was used because of its simple application and reliability.
The dependence of the inhibition eciency, calculated from gravimetric data, on
the concentration of the compounds, c
i
dissolved in 1 M H
2
SO
4
at room temperature
(20 C 1) is presented in Fig. 7. The following conclusions may be drawn on the
basis of this dependence compared to 1 M HCl (Fig. 1):
(1) The compounds investigated have a signicant protective eect in 1 M H
2
SO
4
,
but it is much lower than in 1 M HCl. The maximum inhibiting eect reached is in
the range of 6075% (c = 3:34) while in 1 M HCl it is 8696.5% (c = 729) in the
same concentration range.
(2) The maximum protective eect is obtained at the following concentration
values: 10
2
M for BI, 10
3
M for 2-NH
2
-BI, 2-SH-BI and 1-BBI, 10
5
M for 1,2-
DBBI. On further concentration increase, the IE decreases and the corrosion process
is stimulated. The only exception in this concentration range is observed in case of BI
and 2-SH-BI. This phenomenon is not observed in HCl. The eect described above
can most probably be explained by formation of soluble complexes with the par-
ticipation of the iron ion and the organic compounds present. It is expected to in-
crease rate with the increase in concentration of the organic substances.
(3) The behaviour of 2-SH-BI is of denite interest. Unlike the rest of the com-
pounds investigated, its protective properties do not decrease in 1 M H
2
SO
4
. It is
94% and 95% (c = 20) eective in the presence of 10
4
and 10
3
M solutions, re-
spectively. The values cited completely coincide (IE = 94% and 94.7%, corre-
spondingly) with those obtained in 1 M HCl. This fact provides the evidence that the
mechanism of inhibition achieved with the introduction of this compound diers
50 A. Popova et al. / Corrosion Science 45 (2003) 3358
from that of the process taking place with the participation of the rest of the in-
hibitors and moreover, the nature of the acids anion does not aect it.
On the other hand, it is well known that the protective properties of a cation type
of an inhibitor in H
2
SO
4
can be improved with the addition of halide ions such as
Cl

, Br

, I

to the solution. This results in the observation of a synergistic eect in

the corrosion inhibition [39,42,48,5053,5759].
The experimental fact just described has found dierent explanations:
(1) The anions adsorbed on the metal surface form interconnecting bridges be-
tween the metal atoms and the organic cations and thus facilitate the cations ad-
sorption [54].
(2) Antropov et al. [56] explains the increase of the degree of adsorption of or-
ganic cations in the presence of halide ions with variation of the character of in-
teraction between the adsorbed species. It is known that repulsive forces between the
cations arise at high degrees of surface coverage. In case of adsorption of cations and
anions attractive forces arise which results in the formation of a compact adsorption
layer.
(3) The position of PZC can be useful in interpreting the positive synergistic eect
observed in the corrosion inhibition of iron in sulphuric acid solutions by organic
cations in presence of halide ions [42,48,50,53,55]. Irreversible adsorption of halide
ions proceeds at iron unlike the case with mercury. When irreversible chemisorption
takes place, the charge of the halide ions becomes a part of the charge of the metal
Fig. 7. Dependence of inhibition eciency IE(%) on the concentration of the compound c
i
(M) for mild
steel corrosion in 1 M H
2
SO
4
: (

) BI; (
v
) 2-NH
2
-BI; ( ) 2-SH-BI; (

) 1-BBI; () 1,2-DBBI.
A. Popova et al. / Corrosion Science 45 (2003) 3358 51
surface. Moreover, PZC shifts to more positive values allowing thus the adsorption
of organic cations.
Hence, if the compounds studied adsorb electrostatically as cations in 1 M H
2
SO
4
with the addition of KI, a synergistic eect can be expected. If chemisorption pre-
vails, then KI should have no eect.
Aiming at the verication of the statement above, all investigations in 1 M H
2
SO
4
were repeated, but with the addition of 10
4
M KI. The latter substance (KI) inhibits
the corrosion process and its inhibition eciency at a concentration of 10
4
M is 65%
(c = 2:8). The results obtained in the presence of potassium iodide are shown in Fig.
8. It was seen that the behaviour of the inhibitors changes essentially when compared
to that in 1 M H
2
SO
4
with no KI in the same concentration range. The inhibiting
eect of the compounds increased signicantly and the maximum value reached by
the various compounds is in the range from 85 to 96% (c varies from 7 to 25). It
should be noted that this maximum value is very close to the one obtained at the
same concentration but in 1 M HCl. Neither decrease in the degree of protection, nor
stimulation of the corrosion process are observed, i.e. IE increases with concentra-
tion increase and the corresponding concentration dependence does not go through a
maximum, as in 1 M H
2
SO
4
with no KI. The results obtained resemble in general
those in 1 M HCl.
The behaviour of 2-SH-BI diers again from that of the rest of the inhibitors
studied. Its IE remains unchanged and equals that in 1 M HCl and 1 M H
2
SO
4
. This
shows that its protective properties cannot be aected by the presence of halogen
ions in the solution, i.e. they are not aected by the anion of the medium.
What is the high temperature behaviour of the compounds investigated in 1 M
H
2
SO
4
? The answer to this question would have provided certain information on the
character of their adsorption on the metal surface. High IE could have been expected
at high temperatures in the case of a strong chemisorptive bond.
Fig. 8. Dependence of inhibition eciency IE(%) on the concentration of the compounds c
i
(M) for mild
steel corrosion in 1 M H
2
SO
4
1 10
4
M KI: (

) BI; (
v
) 2-NH
2
-BI; ( ) 2-SH-BI; (

) 1-BBI; () 1,2-
DBBI.
52 A. Popova et al. / Corrosion Science 45 (2003) 3358
Experiments were carried out at 60 C using polarization curves and polarization
resistance methods. Analogous to the investigations in 1 M HCl, the concentration
values, at which maximum inhibiting eect, IE(%) was reached, were determined on
the basis of the concentration curves in Fig. 7. These concentration values were used
in the subsequent experiments. The results obtained are presented in Figs. 9 and 10.
It is seen from Fig. 9 that the curve obtained in 1 M H
2
SO
4
and those in the presence
of BI, 2-NH
2
-BI, 1-BBI and 1,2-DBBI almost coincide. The curve obtained in 2-SH-
BI solution is the only one that diers. It is shifted to the range of smaller corrosion
current densities. The lines characterizing the polarization resistance R
p
in 1 M
H
2
SO
4
and in presence of BI, 2-NH
2
-BI, 1-BBI and 1,2-DBBI are almost parallel,
while that obtained in the 2-SH-BI solution has a considerably greater slope (Fig.
10).
The data indicate that almost all inhibitors lost their protective eect at 60 C.
The values of the corrosion current density j
corr
obtained in their solutions on the
application of both methods are almost equal to those for 1 M H
2
SO
4
with no in-
hibitor present (6360 300 lAcm
2
). The only exclusion is once again observed in
case of 2-SH-BI, i.e. the high inhibiting eect determined by both methods (93.3%) is
in fact equal to that in 1 M HCl at 60 C (93.9%).
All experiments described in this paper lead to the conclusion that the adsorption
model based on the protonated (cation) form of the investigated derivatives of
benzimidazole is more probable. A chemisorption mode of adsorption is more likely
Fig. 9. Polarization curves at 60 C in 1 M H
2
SO
4
(1) and in presence of BI (2), 2-SH-BI (3), 2-NH
2
-BI (4),
1-BBI (5) and 1,2-DBBI (6).
A. Popova et al. / Corrosion Science 45 (2003) 3358 53
for 2-SH-BI. Contradictory ideas concerning the nature of the adsorbed species and
the type of adsorption for organic amines are found in the literature. Some of the
authors [6062] attribute inhibition to chemisorption of neutral species while others
[6366] hold that the organic cation is electrostatically adsorbed. The results we
obtained, with most of the compounds studied, verify the conclusions of the latter
group of authors.
Hence it can be concluded that the adsorption characteristics cannot be simply
elucidated on the basis of the comparison of the apparent activation energy values
obtained in the presence and absence of inhibitors as well as on the basis of the
values of IE(%) at high temperatures.
The high IE observed upon introduction of 2-NH
2
-BI, 1-BBI and 1,2-DBBI to 1
M HCl at high temperatures is most probably due to the cations physical adsorption
favoured by the specically adsorbed Cl

found in the solution. It is known that the

adsorptiondesorption equilibrium is shifted towards desorption upon temperature
increase, but the compounds concentration is high and so a relatively high degree of
coverage [40] is maintained even at high temperatures. The molecular structure,
which takes account of the chemical bonds present and their spatial disposition, is of
importance too. In particular, it determines the dierences observed.
An explanation of the fact that E
a
in the presence of 1-BBI is smaller
(E
a;total
= 56:69 kJ mol
1
) than that in HCl (E
a;total
= 61:39 kJ mol
1
) is found in the
Arrhenius equation (1). The preexponential factor is connected with the active
centres number in case of heterogeneous chemical reactions. Electrochemical cor-
rosion is such a process. The adsorbed inhibitors molecules block an essential part
of the active sites on the metal surface which is energetically inhomogeneous. In
Fig. 10. Polarization resistance method. Dependence of E(mV)j(lAcm
2
) at 60 C in 1 M H
2
SO
4
(1) and
in presence of 2-NH
2
-BI (2), 2-SH-BI (3), 1-BBI (4) and 1,2-DBBI (5).
54 A. Popova et al. / Corrosion Science 45 (2003) 3358
general the adsorbed species block the most active sites, i.e. those with the lowest E
a
value. Thus, sites of higher activation energy, which are in fact greater in number (k
is of a larger value with inhibitor present), take part in the subsequent corrosion
process. In case of 1-BBI, the value of E
a
is less than that in 1 M HCl. The same is
valid for k (k = 1:0 10
11
on 1-BBI introduction when compared to 2:4 10
13
in
pure HCl). It seems that surface sites which are fewer in number, but more active
from a corrosion point of view (they are of lower activation energy) stay unoccupied
when the inhibitor is already adsorbed. This is veried by the data from the im-
pedance studiesthe lowest value of n
d
(0.89) is obtained in the case of 1-BBI, when
compared to that in the presence of 1,2-DBBI and 2-SH-BI, taking into consider-
ation that n
d
measures surface heterogeneity. Therefore, a partial compensation ef-
fect [67,68] can be assumed. This is more often observed when inhibitors of greater,
but more planar molecules are used. They shield both the active and less active sites
on the metal surface. Thus, some active sites (of lower E
a
) are left, and they deter-
mine the value of the apparent activation energy of the corrosion process.
How does the inhibition work?
It is well known that the spontaneous dissolution of iron in acids can be described
by the anodic dissolution reaction
Fe = Fe
2
2e

(8)
accompanied by the corresponding cathodic reaction
2H

2e

= H
2
(9)
The corrosion of iron and steel in uninhibited acidic solutions is controlled by the
hydrogen evolution reaction [1,16,39,56,57].
Following the electrochemical kinetics laws, the rates of the anodic and cathodic
reactions in acidic solutions, in presence of an adsorbed inhibitor on the metal
surface can be described by:
i
a
= k
a
1 ( h) exp
F
RT
zb E (

W
1
)

(10)
i
c
= k
c
H
3
O

[ [ 1 ( h) exp

F
RT
aE [ 1 ( a)W
1
[

(11)
where k
a
and k
c
are the corresponding rate constants, h is the fraction of the electrode
surface covered by the inhibitor, E is the electrode potential relative to solution
potential, W
1
is the potential drop in the outer part of the double layer, a and b are
the symmetry factors of both reactions, while z is the charge of the metal ions in the
solution.
It is assumed that hydrogen ionization as well as the proceeding of electro-
chemical reactions can be neglected on the surface sites covered by the inhibitor.
Besides, it is accepted that the presence of iron cations on the uncovered surface has
almost no eect.
The studied derivatives of benzimidazole aect the rate of the corrosion process
mainly through the variation of the degree of coverage h, i.e. by the blocking eect
A. Popova et al. / Corrosion Science 45 (2003) 3358 55
they exert. As cation inhibitors BI, 2-NH
2
-BI, 1-BBI and 1,2-DBBI block the space
of the OHL. This results in a decrease of the concentration of the hydrogen ions in
the surface layer and hence, of the rate of the corrosion reaction. In case of 2-SH-BI,
for which a chemisorption mode of adsorption or contact adsorption was found
more probable, blocking of the active surface atoms is expected to occur. Most
probably, a coordinative type of a bond arises between iron, having vacant, low-
energy electron orbital and S-heteroatom possessing lone-pair electrons.
Molecules of higher volume, like 1-BBI and 1,2-DBBI, are expected to have better
inhibiting properties (Fig. 1).
The adsorption of the cations in OHL leads to a decrease of W
1
i.e. to its shift to
more positive values. This in turn results in a decrease of the concentration of the
hydrogen ions in the surface layer and a corresponding increase of the overpotential
of hydrogen evolution. Thus a synergistic eect is superimposed to the blocking one.
4. Conclusions
1. All ve diazoles studied have well pronounced inhibiting properties in corrosion
of mild steel in hydrochloric acid. 2-SH-BI. 1-BBI and 1,2-DBBI are particularly
good inhibitors, while 2-SH-BI has protective properties in sulphuric acid as well.
2. The compounds investigated have inhibiting properties at all temperatures stud-
ied. With temperature increase, the IE of BI decreases essentially, that of 2-SH-
BI and of 1,2-DBB decreases slightly, while IE of 1-BBI even increases, although
not so well outlined. There is an adequate change of the apparent activation en-
ergy when compared to that in case of uninhibited corrosion in 1 M HCl.
3. The impedance investigation shows that the rate of corrosion on a surface free
from an inhibitor decrease (R
ct
decreases) as well as the protective action of the
adsorbed inhibitor layer decreases (R
a
decreases) with temperature increase.
4. It is most probable that the inhibiting properties of BI, 2-NH
2
-BI, 1-BBI and 1,2-
DBBI are determined by the electrostatic adsorption of the protonated form of
the compounds which is aected by the anionic composition of the medium.
The chemisorption mode is more probable for 2-SH-BI.
5. The inhibiting action of the compounds investigated is due to the joint blocking
and energetic eect, leading to the decrease of the surface concentration of the hy-
drogen ions and the increase of hydrogen evolution overpotential.
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