Materials Chemistry and Physics 90 (2005) 286297

Synergistic inhibition between OP and NaCl on

the corrosion of cold-rolled steel in phosphoric acid
Xueming Li a , Libin Tang a,b,
a

Department of Chemistry, Yunnan University, Kunming 650091, Peoples Republic of China

b Materials Research and Development Center, Kunming Institute of Physics,
Kunming 650223, Peoples Republic of China
Received 28 February 2004; accepted 21 May 2004

Abstract
The effects of single OP and the mixture of various concentrations of OP and 0.1 M NaCl on the corrosion of cold-rolled steel in 1.03.5 M
phosphoric acid have been investigated by using weight loss method and polarization method. This study revealed that cold-rolled steel
in phosphoric acid has been more efficiently inhibited by OP in the presence of NaCl than single OP, and inhibition efficiency increases
with increasing concentration of OP at the same temperature, but decreases with increasing temperature studied. A synergistic effect exists
when OP and chloride ion are used together to prevent cold-rolled steel corrosion in 1.03.5 M phosphoric acid at every experimental
temperature. The polarization curves showed that OP is a cathodic inhibitor, while the complex of OP and NaCl is a mixed-type inhibitor
that mainly inhibits the cathodic corrosion of the steel. The experimental results suggested that the presence of chloride ion in the solution
stabilized the adsorption of OP molecules on the metal surface and improved the inhibition efficiency of OP. The adsorption of single OP
follows the Langmuir adsorption isotherm, and the adsorption of the complex accords with the Langmuir adsorption isotherm too. Some
thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy have been calculated by employing
thermodynamic equations. Kinetic parameters such as apparent activation energy and pre-exponential factor have been calculated and
discussed. In 1.53.5 M phosphoric acid, the concentration pre-exponential factor and acid concentration constant have been calculated,
and the synergistic effect has been observed too.
2004 Published by Elsevier B.V.
Keywords: Corrosion; Synergistic inhibition; OP; Chloride ion; Cold-rolled steel; Phosphoric acid

1. Introduction
Acid solutions are widely used in industry. The
corrosion of steel in acidic solution receives considerable
concern. Corrosion inhibitors are used to reduce the corrosion rates of metallic materials in these acidic media. Usually, organic compounds containing nitrogen [116], sulphur
[5,11,13,17,18], oxygen [1924] and phosphorus [23,25,26]
are used for inhibitors against the corrosion of steel in acidic
media. Synergistic effects describe the increase in the effectiveness of a corrosion inhibitor in the presence of another
substance in the corrosive medium. Synergistic inhibition
is an effective means to improve the inhibitive force of
inhibitor, to decrease the amount of usage, to diversify the
application of inhibitor in acidic media. It is necessary for
corrosion scientists to discover, explore and use synergism
Corresponding author. Tel.: +86 0871 5105360;
fax: +86 0871 5152601.
E-mail address: tanglibin1@sina.com (L. Tang).

0254-0584/$ see front matter 2004 Published by Elsevier B.V.

doi:10.1016/j.matchemphys.2004.05.012

in the complicated corrosive media. Actually, this phenomenon has been frequently used in practice [8,2629].
The synergistic effects between organic inhibitors and
halide ions on metal corrosion in acidic solution have been
reported by many authors [8,19,27,30]. However, the report
about synergism between surfactants and halide ions on
metal corrosion in phosphoric acid is rare. In this work,
the synergistic inhibition between OP and chloride ion in
phosphoric acid is investigated by means of weight loss
and electrochemical methods, and the possible synergistic
mechanism has been proposed.

2. Experimental
2.1. Materials
The experiments were performed with cold-rolled steel
specimens with the following composition: C 0.10%,
Mn 0.50%, P 0.025%, S 0.025%, Fe remainder.

X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

287

2.2. Solutions
The aggressive solutions used were made of AR-grade
phosphoric acid. Appropriate concentrations of acid were
prepared using distilled water. The concentration range of
OP employed was 0.570.0 M in the absence and presence of 0.1 M NaCl in various concentrations of phosphoric
acid.
2.3. Gravimetric measurements
Prior to experiment, the cold-rolled steel sheets of
30 mm 115 mm 00.5 mm were abraded with a series of emery paper from 220 to 1000 grades. Then, the
specimens were washed several times with distilled water
then with acetone and dried using a stream of air. After weighing accurately, the specimens were immersed in
100 ml beaker, which contained 100 ml different concentrations of phosphoric acid with and without addition of
different concentrations of OP and 0.1 M NaCl. All the
aggressive acid solutions were open to air. After 4 h, the
specimens were taken out, washed, dried and weighed accurately. Then the tests were repeated at different temperatures.
2.4. Electrochemical measurements
For polarization studies, the steel specimen was embedded in PVC holder using epoxy resin with an exposed
area of 1.0 cm2 (0.155 in.2 ) as a working electrode. A
platinum foil was used as an auxiliary electrode. The
reference electrode was a saturated calomel electrode
(SCE) coupled to a Luggin capillary whose tip was located between the working electrode and the auxiliary
electrode.
Before measurement, the electrode was immersed in test
solution at natural potential for ca. 2 h until a steady state
was reached. All polarization measurements were performed
using PARSTAT 2263 Potentiostat/Galvanostat (Princeton
Applied Research) at 25 C under aerated condition, and the
scanning rate was 0.5 mV s1 .

3. Experimental results and discussion

The molecular formula of OP used as inhibitor is shown
as follows:

Obviously, OP contains many oxygen atoms with

lone-pair electrons. Thus, the substance meets the requirements as a good inhibitor.

Fig. 1. Relationship between weight loss and concentration of OP at

different temperatures.

3.1. Effect of single OP on the corrosion of

cold-rolled steel
3.1.1. Effect of concentration of single OP on the weight
loss and corrosion rate of cold-rolled steel
The weight loss of cold-rolled steel in 1.0 M phosphoric
acid in the presence of various concentrations of OP was
determined. The weight loss as a function of concentration
of OP is plotted in Fig. 1 at different experimental temperatures. In all cases, the weight loss decreases with increasing
the concentration of OP. At concentrations above 50.0 M,
increasing inhibitor concentration does not affect the values
of weight loss obviously. Fig. 1 also shows that weight loss
increasing with an increase in temperature at each concentration of OP, while, at concentrations above 50.0 M, the
weight loss of specimen keeps steady at every experimental
temperature basically.
The value of corrosion rate was calculated from the following equation [1,31]:
v=

m1 m2
St

(1)

where m1 is the mass of the specimen before corrosion, m2

the mass of the specimen after corrosion, S the total area of
the specimen, t the corrosion time and v the corrosion rate.
Fig. 2 provides the influence of inhibitor concentration on
the corrosion rate of cold-rolled steel in 1.0 M phosphoric
acid at different temperatures. It can be seen that the change
of corrosion rate with the concentration of OP is similar to
that of weight loss.
3.1.2. Effect of concentration of single OP on the
inhibition efficiency
With the calculated corrosion rate, the inhibition efficiency of inhibitor for the corrosion of steel was obtained
by using the following equation [32]:
E (%) =

v0 v
100
v0

(2)

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X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

Table 1
The values of coverage obtained from the weight loss for different concentrations of OP in 1.0 M phosphoric acid at different temperatures
OP (M)

0.5
1.0
2.0
3.0
5.0
10.0
30.0
50.0
70.0
Fig. 2. Relationship between corrosion rate and concentration of OP at
different temperatures in 1.0 M phosphoric acid.

where v0 and v are the corrosion rates of the specimen in

1.0 M phosphoric acid without and with the addition of inhibitor, respectively.
The variation in inhibition efficiency with concentration
of OP for cold-rolled steel in 1.0 M phosphoric acid at different temperatures is shown in Fig. 3. The results obtained
show that inhibition efficiency increases with increasing inhibitor concentration at all the temperatures studied. At relative lower concentration of OP (0.530.0 M), inhibition
efficiency increases with increasing concentration of OP.
Fig. 3 also shows that at concentrations above 50.0 M, the
changes of concentration and temperature do not affect the
inhibition efficiency markedly.
3.1.3. Adsorption isotherm for single OP
Assuming the corrosion inhibition was caused by the adsorption of OP, and the degree of surface coverage () for
different concentrations of OP in 1.0 M phosphoric acid was
evaluated from weight loss measurement using the Sekine
and Hirakawas method [25]:
v0 v
=
(3)
v0 v m
where vm is the smallest corrosion rate.

Coverage
30 C

35 C

40 C

45 C

0.422
0.639
0.815
0.872
0.910
0.937
0.987
0.923
1.000

0.187
0.411
0.682
0.776
0.845
0.922
1.000
0.977
0.967

0.160
0.325
0.529
0.697
0.780
0.862
0.986
1.000
0.971

0.037
0.183
0.359
0.466
0.577
0.703
0.907
0.998
1.000

The values of coverage have been calculated and listed

in Table 1. Apparently, the value of coverage increases with
an increase in concentration of OP at each experimental
temperature basically.
Assuming that the adsorption of OP on steel surface follows the simplest adsorption isotherm, i.e., the Langmuir
adsorption isotherm, then the Langmuir adsorption isotherm
was applied to investigate the adsorption mechanism by the
following equation [1,3335]:
c
1
= +c

(4)

where k is the equilibrium constant of adsorption process

and c the inhibitor concentration.
The regression between c/coverage and c has been done
using computer, and the corresponding parameters have been
listed in Table 2. Obviously, the linear correlation coefficients and slopes are close to 1.000, which means that the
assumption is correct, i.e., the adsorption of OP on steel surface obeys the Langmuir adsorption isotherm.
Fig. 4 also clearly shows that the good linear relationship
between c/coverage and c at 35 C.
3.1.4. Thermodynamic parameters for single OP
Thermodynamic model can be used to explain the adsorption phenomenon of inhibitor molecule. Using the obtained
adsorption coefficients, the adsorption free energy, adsorption heat and adsorption entropy can be calculated.
The adsorption heat was calculated according to the Vant
Hoff equation [1,34]:
ln k =

Hads
+ constant
RT

(5)

Table 2
Some parameters of the linear regression between c/ and c

Fig. 3. Relationship between inhibition efficiency and concentration of

OP at different temperatures.

Temperature ( C)

30
35
40
45

1.754
9.593
5.867
1.732

106
105
105
105

Slope

Linear correlation
coefficient

1.016
1.008
0.988
0.905

0.999
1.000
1.000
0.992

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289

The negative values of S0 might be explained in the

following way: before the adsorption of inhibitors onto the
steel surface, inhibitor molecules might freely move in the
bulk solution (the inhibitor molecules were chaotic), but
with the progress in the adsorption, inhibitor molecules were
orderly adsorbed onto the steel surface, as a result, a decrease
in entropy [1].

Fig. 4. Dependence of c/coverage on concentration of OP at 35 C.

To obtain the adsorption heat, the regression between ln k

and 1/T was dealt with. Clearly, the adsorption heat can be
obtained by using the slope of the regression. Under the experimental conditions, the adsorption heat can be approximately regarded as the standard adsorption heat (H0 ).
To obtain the standard adsorption free energy (G0 ), the
following equation was employed [1,36]:



1
G0
k=
exp
(6)
55.5
RT
According to the thermodynamic basic equation G0 =
H 0 T S 0 , the standard adsorption entropy, S0 can be
calculated.
All the thermodynamic parameters were obtained and
listed in Table 3.
The negative value of adsorption free energy means that
the adsorption of OP on steel surface is a spontaneous process. Table 3 also shows that the absolute value of adsorption free energy decreases with increasing the experimental
temperature. According to Eq. (6), it can be concluded that
a decrease of the absolute value of adsorption free energy
leads to the reduction in equilibrium constant of the adsorption process. That is to say, with increasing temperature more
and more inhibitor molecules depart from the steel surface.
The negative value of adsorption heat indicates that the
adsorption is an exothermic process, the magnitude of adsorption heat is larger than the common physical adsorption
heat, reaching the common chemical adsorption heat, probably meaning that the chemical adsorption takes place.
Table 3
The thermodynamic parameters of adsorption of different concentrations
of OP on the steel surface at different temperatures in 1.0 M phosphoric
acid
Temperature
( C)

G0
(kJ mol1 )

H
(kJ mol1 )

S0 (J mol1 K1 )

30
35
40
45

46.359
45.578
45.037
42.530

118.923
118.923
118.923
118.923

239.366
238.017
235.944
240.116

3.1.5. Kinetic parameters for single OP

The adsorption phenomenon has been successfully explained by using thermodynamic parameter, to further elucidate the inhibition properties of single OP, the kinetic model
was employed.
The natural logarithm of the corrosion rate (v) can be
represented as a linear function of 1/T, i.e. [1]:
ln v =

Ea
+ ln A
RT

(7)

where Ea represents the apparent activation energy, R the

universal gas constant, T the absolute temperature, and A
the pre-exponential factor. The regression between ln v and
1/T was completed using the computer, and it is found that
all the regression coefficients are close to 1, which means
that the linear relationship between ln v and 1/T is good. The
apparent activation energy and pre-exponential factor can
be calculated from the slope and intercept of the regression,
respectively. All the kinetic parameters were calculated and
listed in Table 4.
Table 4 and Fig. 5 suggest that the apparent activation energy, at relative lower concentration (0.52.0 M), increases
with an increase in concentration of OP, while at a range
from 2.0 to 50.0 M, decreases with increasing concentration of OP as a whole. That is to say, in this system there is
a maximum for the apparent activation energy. The result is
the same as some studies [1].
It is worth noting that the variance in the pre-exponential
factor is similar to the variance in the apparent activation
energy.
The dependence of the apparent activation energy on the
concentration of OP is shown in Fig. 5.

Table 4
Some parameters of the linear regression between ln v (corrosion rate)
and 1/T
OP (M)

Pre-exponential
factor (g m2 h1 )

0.5
1.0
2.0
3.0
5.0
10.0
30.0
50.0
70.0

3.303
1.131
4.134
2.810
1.156
1.464
5.726
3.917
6.002

1015
1017
1018
1018
1018
1017
1014
1010
1012

Ea (kJ mol1 )

Linear regression
coefficient

83.842
93.496
103.530
102.980
101.050
96.153
82.634
57.882
70.954

0.981
0.987
0.996
0.990
0.988
0.985
0.976
0.969
0.992

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X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

Fig. 5. Dependence of apparent activation energy on the concentration of

OP.

Fig. 7. Relationship between corrosion rate and concentration of OP in

the presence of 0.1 M NaCl.

3.2. Effect of OP and NaCl on the corrosion of cold-rolled

steel
3.2.1. Effect of concentration of OP on the weight loss and
corrosion rate of steel in 1.0 M phosphoric acid in the
presence of 0.1 M NaCl
Fig. 6 shows the plot of weight loss against the concentration of OP for cold-rolled steel in 1.0 M phosphoric acid
containing 0.1 M NaCl at different temperatures. It is clear
that at a certain experimental temperature, weight loss of
specimen decreases with an increase of concentration of OP
in the presence of 0.1 M NaCl, and at concentrations above
10 M, with increasing concentration of OP the value of
weight loss does not change remarkably. At a certain concentration of OP, the weight loss of specimen increases with
a rise in the temperature. At relative higher concentration
of OP (above 10 M), the weight loss of specimen keeps
steady at every experimental temperature. Thus, compared
with single OP, the effective concentration of OP used as a
corrosion inhibitor is reduced drastically.
Fig. 7 gives the influence of concentration of OP in the
presence of 0.1 M NaCl on the corrosion rate of cold-rolled
steel in 1.0 M phosphoric acid at different temperatures. It
can be seen that the change of corrosion rate with concentration of OP is similar to that of weight loss.

3.2.2. Effect of concentration of OP on the inhibition

efficiency in 1.0 M phosphoric acid in the presence of 0.1 M
NaCl
Fig. 8 shows the plot of inhibition efficiency against the
concentration of OP for cold-rolled steel in 1.0 M phosphoric acid containing 0.1 M NaCl at different temperatures. It
can be seen from Fig. 8 that with increasing concentration
of OP, there is an increase in inhibition efficiency at all experimental temperatures. Furthermore, Fig. 8 shows that increasing concentration of OP and experimental temperature
do not affect inhibition efficiency obviously at concentration
of OP above 10 M in 1.0 M phosphoric acid containing
0.1 M NaCl, and the value of inhibition efficiency remains
above 90%. Compared with Fig. 3, the inhibition efficiency
of OP has been greatly enhanced by adding 0.1 M NaCl, and
the effect of temperature on the inhibition efficiency is no
longer apparent.
Inhibition efficiencies of OP for cold-rolled steel in 1.0 M
phosphoric acid in the absence and presence of 0.1 M NaCl
at different temperatures are given in Table 5. The inhibition
efficiency of OP increases with a rise in concentration at every temperature studied, both in the absence and presence of
0.1 M NaCl. It is found that single OP shows good inhibition
efficiency at relative higher concentration (above 50.0 M),
however, the complex of OP and 0.1 M NaCl has a better

Fig. 6. Relationship between weight loss and concentration of OP in the

presence of 0.1 M NaCl.

Fig. 8. The relationship between inhibition efficiency and concentration

of OP in the presence of 0.1 M NaCl.

X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

291

Table 5
Inhibition efficiency obtained from the weight loss method for different
concentrations of OP without and with the addition of 0.1 M NaCl in
1.0 M phosphoric acid at different temperatures

Table 6
The values of coverage obtained from the weight loss for different concentrations of OP with the addition of 0.1 M NaCl in 1.0 M phosphoric
acid at different temperatures

OP (M)

OP (M)

NaCl (M)

Inhibition efficiency (%)

30 C

35 C

40 C

45 C

0.5
1.0
2.0
3.0
5.0
10.0
30.0
50.0
70.0

0
0
0
0
0
0
0
0
0

33.361
50.466
64.407
68.872
71.895
74.027
77.938
72.917
78.982

15.115
33.335
55.248
62.912
68.451
74.715
81.046
79.146
78.389

12.585
25.647
41.682
54.904
61.481
67.922
77.675
78.800
76.542

2.833
14.052
27.611
35.856
44.395
54.111
69.810
76.757
76.947

0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1

43.016
72.233
80.106
84.132
86.161
87.435
90.859
90.912
92.399
92.652

37.870
68.385
80.493
86.048
87.690
88.922
90.807
93.329
94.014
92.175

33.018
64.043
82.909
86.041
86.150
89.643
91.203
92.748
92.629
94.175

31.856
52.257
69.711
85.000
85.461
87.092
90.971
92.652
93.138
93.224

0.5
1.0
2.0
3.0
5.0
10.0
30.0
50.0
70.0

inhibition efficiency (IE) at lower concentration (10.0 M),

that is to say, the addition of NaCl further increases the
inhibition efficiency values. For example, at 40 C 1.0 M
OP has 25.647% IE and 0.1 M NaCl has 33.018% IE. Their
complex has 82.909% IE, which is bigger than the summation of the first one and the second one. This suggests that
there is a synergistic effect between OP and NaCl. It can be
seen from Table 5 that at low concentration of OP (below
10.0 M), the higher the temperature, the more obvious the
synergistic effect.
3.2.3. Adsorption isotherm for the complex of OP and
chloride ion
Assuming the corrosion inhibition was caused by the adsorption of OP and NaCl, the degree of surface coverage ()
for different concentrations of OP in the presence of 0.1 M
NaCl in 1.0 M phosphoric acid was evaluated from weight
loss measurement using the Sekine and Hirakawas method
[25].
The values of coverage are obtained and listed in Table 6.
From Table 6, it can be seen that the surface coverage degree increases with increasing the concentration of OP at all
temperatures studied. On the other hand, the values of coverage do not be affected markedly by increasing temperature
at a certain concentration of OP.
With the obtained values of coverage, the regression between c/coverage and c at different temperatures has been
completed using computer. Fig. 9 is the relationship between
c/coverage and c at 45 C. The straight line means that there
is a good linear relationship between c/coverage and c, suggesting that the experimental data can be explained by the
Langmuir adsorption isotherm.

0.5
1.0
2.0
3.0
5.0
10.0
30.0
50.0
70.0

NaCl (M)

0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1

Coverage
30 C

35 C

40 C

45 C

0.650
0.785
0.854
0.889
0.911
0.969
0.970
0.996
1.000

0.727
0.856
0.915
0.933
0.946
0.966
0.993
1.000
0.980

0.558
0.835
0.881
0.882
0.934
0.956
0.979
0.977
1.000

0.323
0.612
0.864
0.872
0.899
0.963
0.991
0.999
1.000

Fig. 9. Dependence of c/coverage on concentration of OP in the presence

of 0.1 M NaCl at 45 C.

The obtained adsorption coefficients, slopes, and linear correlation coefficients from the regressions between
c/coverage and c are listed in Table 7. It is shown that all
the linear correlation coefficients are equal to 1.000 and
all the slopes are close to 1, the good linear relationship
between c/coverage and c also indicates that the adsorption
of inhibitor onto steel surface accords with the Langmuir
adsorption isotherm.
3.2.4. Thermodynamic parameters for the complex of OP
and NaCl
To obtain the adsorption heat, the regression between ln k
and 1/T was dealt with. Clearly, the adsorption heat can
be obtained by using the slope of the regression, and the
relationship between ln k and 1/T is shown in Fig. 10.
Table 7
Some parameters of the linear regression between c/ and c for OP in
the presence of 0.1 M NaCl
Temperature ( C)

30
35
40
45

2.432
4.002
2.582
1.672

106
106
106
106

Slope

Linear correlation
coefficient

0.997
0.984
1.002
0.990

1.000
1.000
1.000
1.000

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X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

Table 9
Some parameters of the linear regression between ln v (corrosion rate)
and 1/T in the presence of 0.1 M NaCl

Fig. 10. The relationship between ln k and 1/T.

Fig. 10 indicates the approximate linear relationship

between ln k and 1/T. The adsorption heat was calculated
according to the Vant Hoff equation. Under the experimental conditions, the adsorption heat can be approximately
regarded as the standard adsorption heat (H0 ).
For the OP in the presence of 0.1 M NaCl, all the obtained
thermodynamic parameters are summarized in Table 8. The
negative values of G0 indicates the spontaneous adsorption of inhibitor on the surface of cold-rolled steel. The negative values of G0 also show the strong interaction of the
inhibitor molecules on the cold steel surface [37,38]. Compared with Table 3, the values in Table 8 show that in the
solution containing 0.1 M NaCl the absolute value of adsorption free energy at each experimental temperature is bigger.
The result leads to an increase in the equilibrium constant of
adsorption in solution containing OP and NaCl, which means
that more inhibitor molecules adsorb onto the steel surface
compared with single OP at the same experimental temperature. Therefore, it can be seen that inhibition effect of OP
has been strengthened by a long way due to existing of NaCl.
The negative values of adsorption heat suggest that the
adsorption of inhibitor molecule onto the steel surface in
phosphoric acid is an exothermic process. The driving force
for the adsorption is the decrease in enthalpy rather than
the increase in entropy. The magnitude of adsorption heat
is between heat of liquefaction and chemical reaction heat,
which probably means that the existence of both physical
adsorption and chemical adsorption.
The negative values of adsorption entropy indicate that
the adsorption is a process accompanied by a reduction in
entropy.

OP (M)

Pre-exponential
factor (g m2 h1 )

0.5
1.0
2.0
3.0
5.0
10.0
30.0
50.0
70.0

5.239
5.960
1.416
1.958
3.386
1.554
6.457
1.036
6.846

1016
1014
1011
1012
1011
1011
109
1011
109

Ea (kJ mol1 )

Linear regression
coefficient

93.213
82.956
62.357
69.334
65.197
63.848
56.104
63.487
56.482

0.988
0.931
0.981
0.992
0.959
0.980
0.978
0.995
0.919

3.2.5. Kinetic parameters for the complex of OP and NaCl

The regression between ln v and 1/T was completed using
computer, and it is found that all the regression coefficients
are close to 1, which means that the linear relationship between ln v and 1/T is good. The apparent activation energy
and pre-exponential factor can be calculated from the slope
and intercept of the regression, respectively. All the kinetic
parameters were calculated and listed in Table 9.
Table 9 shows that the apparent activation energy acts
as a variable of the concentration of OP. The relationship
between the apparent activation energy and concentration of
OP is shown in Fig. 11.
3.3. Polarization studies
3.3.1. Polarization curve of single OP
The polarization behavior of cold-rolled steel in 1.0 M
phosphoric acid in the absence and presence of different
concentrations of OP is shown in Fig. 12. Electrochemical
parameters such as corrosion current density (icorr ), corrosion potential (Ecorr ) and Tafel slopes are given in Table 10.
Fig. 12 shows that the addition of OP to 1.0 M phosphoric acid shifts the polarization curves to more negative values. The corrosion potential moves in the negative direction
obviously with the addition of OP. This result suggests that
the hydrogen evolution reaction is retarded by the addition
of OP. In the aerated acid solutions, cathodic currents are

Table 8
The thermodynamic parameters of adsorption of different concentrations
of OP with the addition of 0.1 M NaCl on the steel surface at different
temperatures
Temperature
( C)

G0
(kJ mol1 )

H0
(kJ mol1 )

S0
(J mo1 K1 )

30
35
40
45

47.183
49.237
48.896
48.526

24.571
24.571
24.571
24.571

74.592
80.047
77.678
75.297

Fig. 11. The relationship between Ea and concentration of OP in the

presence of 0.1 M NaCl.

X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

293

Fig. 12. Polarization curves for various concentration of OP in 1.0 M

phosphoric acid tested at 25 C.

attributed to the sum of two partial cathodic currents: the

hydrogen evolution and the reduction of dissolved oxygen
in the solution [39,40], the later does not depend on the concentration of inhibitor [40]. From results given in Table 10,
an obvious shift of corrosion potential (Ecorr ) towards more
negative values compared with that of 1.0 M phosphoric acid
is observed. These results indicate that OP primarily behaves
as a cathodic inhibitor.
3.3.2. The polarization curve for synergistic inhibition
The inhibition efficiency may be calculated by corrosion
current density using the following formula [37]:
E (%) =

100(icorr i corr )
icorr

(8)

where icorr and i corr are the corrosion current densities in the
absence and presence of inhibitor, respectively. The values
of inhibition efficiency are listed in Table 11.
Fig. 13 clearly indicates that the cathodic reaction is inhibited by the presence of 0.1 M NaCl. In the presence of
the mixture of OP and NaCl, however, both anodic and caTable 10
Electrochemical parameters of OP obtained from polarization measurements in 1.0 M phosphoric acid at 25 C
OP
(M)

Ecorr (mV vs.

SCE)

icorr
(A cm2 )

0
0.5
2.0
10.0

465.131
484.420
491.043
487.334

1.406
2.831
2.338
2.103

102
102
102
102

c (mV dec1 )

a (mV dec1 )

91.208
109.592
115.350
119.271

20.537
33.366
40.473
38.500

Fig. 13. Polarization curves for various kinds of inhibitor in 1.0 M phosphoric acid tested at 25 C.

thodic reactions are dramatically inhibited. The corrosion

potential for the mixture of OP and NaCl is slightly shifted
to cathodic direction, meaning that the mixture behaves as
a mixed-type inhibitor that mainly inhibits the cathodic corrosion of the steel in 1.0 M phosphoric acid.
Fig. 13 suggests that with the addition of NaCl, OP acts as
an excellent inhibitor for steel corrosion in phosphoric acid,
showing that there is a strong synergistic inhibition between
OP and NaCl, the result is in agreement with that obtained
from the weight loss technique.
The electrochemical parameters have been calculated and
listed in Table 11. Apparently, the inhibition efficiency calculated from corrosion current density for the mixture reaches
a considerable value (88.620%). There is a small difference
in the inhibition efficiencies calculated from the corrosion
current density and the weight loss method (corrosion rate).
This may be the result of the difference in the two methods.
The data obtained from weight loss method are average values, while the data obtained from electrochemical techniques
are instantaneous values. Another possible reason may be
the difference in the temperature. The electrochemical experiment was carried out at 25 C, while the weight loss ex-

294

X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

Table 11
Electrochemical parameters of the mixture of OP and NaCl obtained from polarization measurements in 1.0 M phosphoric acid at 25 C
NaCl (M)
0
0.1
0.1
0.1
0.1

OP (M)

Ecorr (mV vs. SCE)

0
0
0.5
2.0
10.0

465.131
458.943
473.616
469.847
465.218

icorr (A cm2 )
1.406
5.630
2.803
1.600
1.805

periment was carried out at temperatures ranging from 30

to 45 C.
3.4. Effect of 2 3 M OP and 0.1 M NaCl on the corrosion
of steel in 1.533.5 M phosphoric acid
Generally speaking, both experimental temperature and
acid concentration can affect the corrosion rate of metal.
The relationship [v = A exp(Ea /RT)] between corrosion
rate (v) and experimental temperature (T) has been widely
used by the corrosion scientists [6,19,2225], as for the relationship between corrosion rate (v) and acid concentration;
however, only Mathurs [41] empirical equation has been
diffusely used. Many studies [42,43] show that there is an
exponential relationship between the corrosion rate and the
acid concentration.
In order to investigate the effect of phosphoric acid concentration on the corrosion of steel, an empirical equation
has been employed, i.e.
v = N exp(Bc)

(9)

where v is the corrosion rate, N is defined as the concentration pre-exponential factor, B is defined as the acid concentration constant, and c is the acid concentration.
Eq. (9) can be written as
ln(v) = ln(N) + Bc

102
101
101
101
101

c (mV dec1 )

a (mV dec1 )

IE (%)

91.208
114.244
96.798
93.012
94.519

20.537
13.751
28.698
27.265
23.988

0
59.957
80.064
88.620
87.162

17.670 g mm2 h1 at 40 C, respectively. With the addition of the mixture of 0.1 M NaCl and 2 M OP, however,
the concentration pre-exponential factor (N) drastically decreases to 3.224 g m2 h1 . This may be the indication of
the presence of synergistic inhibition. At other experimental
temperatures, the change of N is similar to that at 40 C.
Eq. (9) also indicates that there is an exponential relationship between the acid concentration constant (B) and corrosion rate (v), which means that a small variation in acid concentration constant (B) may cause an obvious change in corrosion rate (v). For 1.53.5 M phosphoric acid at 40 C, the
blank acid concentration constant equals 0.273 M1 , while
for 1.53.5 M phosphoric acid in the presence of 0.1 M NaCl,
the value of B is equal to 0.188, which is smaller than that
of the blank (0.273 M1 ). The change of the value of B
leads to the decrease in corrosion rate. At other experimental
temperatures, the same change has been observed. Therefore, for 1.53.5 M phosphoric acid in the presence of 0.1 M
NaCl, both the decreases in B and N can cause the reduction
in corrosion rate. As far as the systems of 1.53.5 M phosphoric acid in the presence of 2 M OP with and without
addition of 0.1 M NaCl are concerned, the values of B are
bigger than those of the blanks at all experimental temperatures. This indicates that in these systems, the reduction of
corrosion rate is mainly decided by the decrease in N rather
than the decrease in B.

(10)

Fig. 14 clearly shows that the regression between ln(v)

and c gives a straight line with the intercept of ln(N) and
slope of B. The calculated concentration pre-exponential factor (N), acid concentration constant (B) and regression coefficient (r) are listed in Table 12.
The regression coefficients listed in Table 12 are close to
1, which indicates that there is a good linear relationship
between the natural logarithm of corrosion rate (v) and acid
concentration (c), the good linear relationship between ln(v)
and acid concentration is also proved by Fig. 14. Eq. (9)
indicates that the concentration pre-exponential factor (N)
is directly proportional to corrosion rate (v), meaning that
the higher the value of N, the bigger the value of corrosion
rate. Table 12 obviously suggests that in the presence of inhibitors, there is a decrease in concentration pre-exponential
factor (N), leading to the decrease in corrosion rate. In the
presence of single 0.1 M NaCl and single 2 M OP, the
concentration pre-exponential factors (N) are 20.016 and

Fig. 14. Relationship between ln v and concentration of phosphoric acid

in the absence and presence of various kinds of inhibitors at 40 C.

X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

295

Table 12
Some parameters of the linear regression between ln(v) and c
T ( C)

Solution

N (g m2 h1 )

B (M1 )

30

1.53.5 M
1.53.5 M
1.53.5 M
1.53.5 M

phosphoric
phosphoric
phosphoric
phosphoric

acid
acid + 0.1 M NaCl
acid + 2 M OP
acid + 2 M OP + 0.1 M NaCl

12.217
8.514
4.112
1.899

0.307
0.218
0.577
0.335

0.994
0.991
0.990
0.966

35

1.53.5 M
1.53.5 M
1.53.5 M
1.53.5 M

phosphoric
phosphoric
phosphoric
phosphoric

acid
acid + 0.1 M NaCl
acid + 2 M OP
acid + 2 M OP + 0.1 M NaCl

20.141
15.568
12.103
2.482

0.280
0.198
0.431
0.527

0.998
0.995
0.992
0.988

40

1.53.5 M
1.53.5 M
1.53.5 M
1.53.5 M

phosphoric
phosphoric
phosphoric
phosphoric

acid
acid + 0.1 M NaCl
acid + 2 M OP
acid + 2 M OP + 0.1 M NaCl

27.976
20.016
17.670
3.224

0.273
0.188
0.387
0.586

0.999
0.995
0.995
0.993

45

1.53.5 M
1.53.5 M
1.53.5 M
1.53.5 M

phosphoric
phosphoric
phosphoric
phosphoric

acid
acid + 0.1 M NaCl
acid + 2 M OP
acid + 2 M OP + 0.1 M NaCl

42.811
35.280
33.037
11.964

0.269
0.185
0.377
0.426

0.997
0.992
0.996
0.985

3.5. Effect of phosphoric acid concentration on corrosion

rate of steel
Fig. 15 indicates that corrosion rate increases with the increase in concentration of phosphoric acid in the absence
and presence of inhibitor. For the acid solution with the addition of single OP, the acid concentration affects the corrosion rate prominently, while for the acid solution containing
single NaCl the corrosion rate does not change too much
with increasing the acid concentration. In 1.53.5 M phosphoric acid, the corrosion rate for the solution with the addition of single OP is bigger than that for the solution with the

addition of single NaCl. Furthermore, the corrosion rate for

the solution in the presence of single OP is close to that of
the blank, which indicates that 2 M OP has weak protection against steel corrosion with an increase in acid concentration. Combined with NaCl, however, the corrosion rate
of OP is the smallest compared with the corrosion rates of
the blank, single OP and single NaCl, which suggests that
the presence of NaCl can strengthen the protection of OP
against the steel corrosion.
3.6. Effect of phosphoric acid concentration on inhibition
efficiency
The relationship between inhibition efficiency and phosphoric acid concentration is shown in Fig. 16. It is obvious
that inhibition efficiency for single 0.1 M NaCl increases
with an increase in acid concentration, however, inhibition
efficiency for single 2 M OP rapidly decreases with an increase in acid concentration. It can be deduced that in 4.0 M
phosphoric acid, 2 M OP may lose its protection totally. In
Fig. 16,  represents the summation of the inhibition efficiency for single 0.1 M NaCl and single 2 M OP. Clearly,
the summation of inhibition efficiency is smaller than that
of the mixture of 0.1 M NaCl and 2 M OP ( represents
the inhibition efficiency of the mixture), this is the result of
the synergistic inhibition between OP and NaCl.
3.7. Explanation for synergism

Fig. 15. Dependence of corrosion rate on concentration of phosphoric

acid at 40 C.

It is well known that OP is a kind of nonionic surfactant, which contains many oxygen atoms with the two sets
of lone-pair electrons. In neutral aqueous solution, it exists
in the form of neutral molecule, in acidic solution, however,
OP may be protonated, leading to the positive charge in the
molecule. It is also well known that steel surface charges pos-

296

X. Li, L. Tang / Materials Chemistry and Physics 90 (2005) 286297

Fig. 16. Dependence of inhibition efficiency on concentration of phosphoric acid at 40 C.

itive charge because of Ecorr Eq=0 (zerochargepotential) >

0, thus, it is difficult for the positively charged OP to approach the positively charged steel surface due to the electrostatic repulsion, this is why single OP cannot act as an
excellent inhibitor for steel corrosion in acidic solution without containing halide ions. With the presence of halide ions,
the specific adsorption of halide ions causes the negatively
charged surface of steel, thus, by means of electrostatic
attraction (physical adsorption), protonated OP can easily
reaches steel surface, followed by the transference of electron from oxygen atom to the d-orbital of iron atom (chemical adsorption) at the steel/solution interface. This is the
reason that the chemical adsorption occurs in the presence
of single OP, and with the addition of NaCl, both physical
and chemical adsorptions occur, which is in good agreement
with the experimental data.
It is worth noting that polycentric adsorption may take
place as the result of the existence of many oxygen atoms
in one OP molecule.
Another possible reason for the synergism is that the addition of chloride ion in aqueous solution reduces the amount
of the free water molecule, leading to the increase in the
active concentration of OP in solution.

4. Conclusions
From the weight loss and electrochemical studies, it can
be easily concluded that as follows.
OP acts as a cathodic inhibitor for steel corrosion in 1.0 M
phosphoric acid, the inhibition efficiency increases with increasing concentration, but decreases with an increase in

experimental temperature. The adsorption of OP is a spontaneous process, and the process is an exothermic process
accompanying a decrease in entropy.
In 1.0 M phosphoric acid, the adsorption of OP on steel
surface follows the Langmuir adsorption isotherm, only
chemical adsorption occurs. With the addition of 0.1 M
NaCl in 1.0 M phosphoric acid, the adsorption of OP also
accords with the Langmuir adsorption isotherm, both physical and chemical adsorptions occur.
With the addition of 0.1 M NaCl in 1.53.5 M phosphoric
acid, the inhibition efficiency increases with an increase in
concentration of phosphoric acid. The synergistic effect between OP and NaCl is observed. The mixture can be used as
an excellent inhibitor for steel corrosion in phosphoric acid
over a wide temperature range.
Compared with single OP, the complex of OP and NaCl
exhibits a stronger tendency to adsorb onto steel surface,
since the absolute values of adsorption free energy for the
complex are bigger than those for single OP.
Single OP acts as a cathodic inhibitor against steel corrosion in phosphoric acid, the mixture of OP and NaCl behaves
as a mixed-type inhibitor that mainly inhibits the cathodic
corrosion of the steel. The presence of NaCl can drastically
improve the inhibition efficiency of OP. This may be the
result that the presence of NaCl stabilize the adsorption of
OP, indicating there is a synergistic inhibition for the steel
corrosion in phosphoric acid.
The synergistic inhibition between OP and NaCl exists
over a wide concentration range of phosphoric acid.
The experimental data can satisfactorily explained by the
empirical concentration equation, which has been put forward by the authors.
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