Indian Journal of Chemical Technology

Vol.18, July 2011, pp 291-300

Corrosion behaviour of mild steel in aqueous acetic acid solutions containing

different amounts of formic acid
S K Singha, A K Mukherjeeb* & M M Singhb
a
Department of Chemistry, University of Delhi, Delhi 110 007, India
b
Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi 221 005, India
Received 26 April 2010; accepted 7 June 2011
The kinetics of mild steel corrosion in 20:0, 19:1, 18:2 and 15:5 (v/v%) aqueous mixture of acetic and formic acids has been
investigated by weight loss and potentiostatic polarization techniques. The effects of composition of electrolyte and temperature
on the corrosion rate of mild steel have been evaluated. The corrosion rate of mild steel increased linearly with temperature as
well as amount of formic acid in the mixture. Anodic polarization curves exhibited active nature over the whole range of
potential at each composition and temperature. Addition of sodium acetate to the mixture led to the transition from active to
active-passive-transpassive behaviour in the solutions having lower concentration of formic acid. On replacing sodium acetate
by sodium formate, and sodium sulphate, no change in the nature of polarization behaviour is observed.
Keywords: Mild steel, Acetic acid, Formic acid, Passivity, Corrosion

Organic acids belong to the group of the most
important chemicals used in several industries such as
textile, leather, chemical and food, pulp and paper,
drugs and pharmaceuticals, plastics and fibres,
refineries and petrochemicals. These acids are used as
reagents for the manufacture of various chemicals
ranging from drugs and pharmaceuticals to plastics and
fibres1-5. Most of these acids are produced more as
precursors for the other chemicals than for end use as
acids themselves. Acetic and formic acids are used as
chemical intermediates (e.g. vinyl acetate monomer,
cellulose acetate, acetic anhydride, chloroacetic
acid and terephthalic acid). These acids are used in
textile, leather, dye, rubber, nylon, plastic, paint,
pharmaceuticals and medicines, food, pesticide,
herbicide, bactericide, fungicide, agriculture, poultry,
oil, pulp and paper, flavour and perfume, photography,
chemical manufacturing and steel industries. Formic
acid is used more as an environmentally benign storage
and transportation medium for hydrogen, the clean
energy of the future6-17. Acetic and formic acids are
more frequently used as reactants or solvents in many
industrial processes18. These two acids are produced
during the glycol oxidation degradation process19.
A lot of acetic acid is also produced during the anodic
polarization of titanium in ethanol causing rapid
decrease in pH value, and resulting in stress corrosion
cracking of the metal20. Among other impurities, formic
acid is the major constituent present in acetic acid5,6,21.
storage tanks for industries that either manufacture
*Corresponding author (E-mail address: ashim.apc@itbhu.ac.in)
Formic acid is the most aggressive among all
pure organic acids1,22-23. Acetic acid is slightly less
corrosive in its pure form, but has been found to
play a major role in certain corrosion systems24,25.
CO2 corrosion of carbon steel pipelines24 in the
presence of acetic acid was studied using artificial
pit electrode assembly. The results gave strong
and complementary evidence about the major role
played by acetic acid in the growth mechanism
of localized attacks in CO2 corrosion. The corrosion
behavior of an iron-copper composite has been
investigated in different electrolytic solutions (sodium
chloride, hydrochloric, acetic or sulfuric acids)25.
The parameters obtained in acetic acid and sodium
chloride are higher than those corresponding to
hydrochloric or sulfuric acids. With the exception of
formic acid which is highly ionized, other organic
contaminants found in the usual acetic acid process
stream only serve to dilute the acid and reduce
its corrosivity26. The various aspects of corrosion
behaviour of different metals and alloys in acetic-
formic acid mixtures and their vapours have been
investigated adequately in literature27-32.
It is well known that mild steel is one of the best
preferred materials for industry due to its easy
availability and its excellent physical properties. It is
cheaper than wrought iron and stronger and more
workable than cast iron. Mild steel is used in the
fabrication of containers such as reaction vessels and
or use formic acid as reactant33. Mild steel may be
292 INDIAN J. CHEM. TECHNOL., JULY 2011
considered for storage and transportation of dilute
acetic acid below 50% at room temperature if
relatively higher corrosion rate and iron pick up can
be tolerated8. Mild steel comes in contact with acetic
and formic acids in oil and gas production and their
transportation34,35, petroleum refineries35,36, oil field
pipelines22,24,37, automotive engines using methanol
fuel38, sugar industry etc.39-41 In internal combustion
engines using bio-oil, the formic and acetic acids
present in bio-oil have been reported to be the main
cause of corrosion of mild steel and aluminium42.
Formic acid is found in citrus fruits along with other
organic acids43. Mild steel material is often exposed
to juice or used to package juice44. However, its use
in acidic environments is restricted because of its
susceptibility towards corrosion. Corrosion behaviour
of mild steel in aqueous solutions of acetic and formic
acids have been studied by Singh and Gupta45,46. In
both cases, 20% solution has been reported to show
maximum corrosion rate of mild steel. We have
recently established the corrosivity of acetic47 and
formic acid48 individually, on mild steel. The effect of
temperature, acid concentration and time of exposure
on the corrosion rate has been thoroughly studied.
These parameters have a marked influence on the
corrosion rate of mild steel. 20-25% concentration
of acids has been found to be the most corrosive. The
influence of formic acid on the corrosion behaviour
of mild steel in glacial acetic acid has also been
studied earlier49 and acceleration in corrosion rate
with increase in the amount of formic acid has been
observed. In another study the corrosion of mild
steel in aqueous solution of formic acid containing
different amounts of acetic acid in total 20% acid
composition was found to exhibit interesting results50.
The dissolution of the mild steel in formic acid was
inhibited in the presence of acetic acid. In this context
it was deemed fit to study the effect of formic acid
on the corrosion behaviour of mild steel. In the
present communication, the corrosion behaviour of
mild steel in acetic-formic acid mixtures of various
compositions has been investigated.
Experimental Procedures
AR grade glacial acetic acid and formic acid were
used for weight loss studies. In addition, for
polarization studies sodium acetate (CH3COONa),
sodium formate (HCOONa) and sodium sulphate
(Na2SO4) were also used. CH3COONa, HCOONa and
Na2SO4 were crystallized and dried under reduced
pressure. Double distilled water was used to prepare
the solutions. The solutions were prepared for
composition mixtures of acetic and formic acid in
the ratio 20:0, 19:1, 18:2 and 15:5 (%v/v). Mild steel
specimens having chemical composition in wt%
(C, 0.23; Mn, 0.11; Si, 0.02; P, 0.02; S, 0.02; Ni, 0.02;
Cu, 0.01; Cr, 0.01; Fe, remainder) were used. For
the weight loss experiments the mild steel specimens
of size 3 3 0.1 cm were polished successively
with 1/0-4/0 grade emery papers, washed with soap
water followed by running tap water and finally
with distilled water. These were degreased by
immersing in acetone, dried and stored in a vacuum
desiccator. The samples were kept immersed in
300 mL test solution in glass beakers in static
condition for a specified period of time. The samples
were kept in the beaker in such a way that both
the surfaces were in contact with the solution.
After removing the specimens from the electrolyte
they were washed thoroughly and dried as before.
The corrosion rate was determined from the
difference in weight of the sample before and after
conducting the corrosion study.
For polarization experiments the specimens were
cut into pieces of 3 1 0.1 cm. The experiment was
performed in 100 mL test solution kept in unstirred
condition. The polarization experiments were carried
out in a three-necked pyrex glass assembly with a
working electrode of 2 cm2 exposed surface area of
both sides (inclusive of edges), a platinized platinum
electrode (1 1 cm) as counter electrode and SCE
(saturated calomel electrode) containing KNO3 salt
bridge with a Luggin capillary as reference electrode.
The saturated calomel electrode consisted of Hg2Cl2
paste in Hg and saturated solution of KCl. Only
the luggin capillary contained saturated KNO3
solution in agar-agar gel. KNO3 was used to make
sure that there is no chloride contamination, which
may have caused localized attack leading to pitting
corrosion. All potentials were measured against
SCE. For potentiostatic studies a Wenking model
POS 73 potentiostat was used. The potential was
manually changed in step-wise fashion at a rate of
10 mV/min. At first, a potential across the working
and reference electrodes was applied in such a way
that the current becomes zero and this potential
is defined as OCP (open circuit potential). After
determining the OCP, the potential was initially
applied in the cathodic direction until fast evolution of
bubbles on the surface of the electrode is observed.
The corresponding steady state current densities
were measured directly from the ammeter on the
 SINGH et al.: CORROSION BEHAVIOUR OF MILD STEEL IN AQUEOUS ACETIC ACID
panel of potentiostat. After this the potential
was switched off and brought back to OCP. The
polarization study was carried out in the anodic
direction with respect to OCP. In anodic direction
the potential is increased until the fast dissolution
of material takes place. Each polarization curve
was separately drawn on a larger scale and it was
observed that these curves are linear over the range
50 to 250 mV on each side of the OCP.
All the experiments were conducted in an air
thermostat with a fluctuation of 0.2C in the
constant temperature. The conductivity of the test
solutions at different temperatures was also measured
by ESICO Model 1601E conductometer. pH was
measured by Control dynamics pH meter Model
APX 175 E/C. The surface of the specimens before
and after completion of the experiment has been
examined by SEM technique by JEOL-JSM 840
Scanning Microscope. The corrosion product was
removed and the samples were coated with gold
before SEM analysis.
Results and Discussion
Corrosion behaviour by weight loss method
The weight loss study of mild steel in mixtures of
acetic and formic acid in the ratio 20:0, 19:1, 18:2 and
15:5 (%v/v) have been performed at different
temperatures. The corrosion rates of mild steel as a
function of fraction of formic acid in the mixture of
formic acid with acetic acid at 25, 35 and 45C have
been plotted in Fig. 1. It was observed from the nature
of the curves in the figure that there is a continuous
increase in the corrosion rate with increase in the
amount of formic acid in the mixture. The nature of
the curves obtained in different compositions at the
three temperatures exhibited similar trends.
The observed gradual increase in corrosion rate
with increase in the fraction of formic acid seems to
be obvious in view of the difference in their
corrosivity. The corrosion rate of mild steel at each
concentration of formic acid has been found to be
greater than that in acetic acid. However, the observed
rate in any mixture is not equal to the algebraic sum
of the rates in individual acids. Taking 15:5 (%v/v)
mixture as an example it may be shown that the
observed rate 132.27 mpy is lower than 194.84 mpy
in 5% formic acid and much higher than 60 mpy in
15% acetic acid. This value is not even equal to the
mean value, i.e., 127.42. Thus, it may be concluded
that in a mixture the two acids do not act
293
independently, but corrosivity of one acid is
influenced by the presence of the other acid.
It was observed that a much lower corrosion rate
of mild steel in acetic acid45,47 is obtained than for
the same concentration of formic acid46,48. It has been
already reported that carboxylic acid aggressiveness
increases as the number of carbon atoms in the
alkyl chain decreases6. The presence of formic acid
suppresses the dissociation of acetic acid, thereby
reducing the contribution of acetic acid towards
the total conductance of the mixture. In addition,
the increased viscosity of the medium due to
undissociated acetic acid molecules decreases
the conductance of the mixture even below the
conductance of 5% formic acid. This explains the
observed corrosion rate in 15:5 mixtures which
is even lower than that of 5% formic acid. The
same logic could be extended for other mixture
compositions. The increase in corrosion rate with
rise in temperature likewise can be explained in terms
of increase in conductance of the mixture as a result
of simultaneous increase in the degree of dissociation
of both the acids.
Electrochemical polarization behaviour
The potentiostatic polarization behaviour of mild
steel in varying composition mixtures of acetic and
formic acid in the ratio 20:0, 19:1, 18:2 and 15:5
(%v/v) was investigated at different temperatures.
In Fig. 2, the anodic and cathodic polarization curves
Fig. 1Variation of corrosion rate and conductance with the
fraction of formic acid composition in acetic formic acid
mixtures of total 20% composition at different temperatures: ()
corrosion rate at 25C, () corrosion rate at 35C, () corrosion
rate at 45C, (o) conductance at 25C, () conductance at 35C
and () conductance at 45C
294 INDIAN J. CHEM. TECHNOL., JULY 2011

for various compositions are illustrated at 35C. The
nature of these curves in the mixture of the two acids
is exactly the same as that obtained for formic acid
containing some acetic acid50. The shift in
polarization curves with increase in the amount of
formic acid in acetic acid is marginal
and is in accordance with expectations. Formic
acid being more corrosive than acetic acid, any
addition of formic acid to acetic acid is bound to
increase the corrosion rate of mild steel.
The values of corrosion parameters corrosion
current density (Icorr), corrosion potential (Ecorr), the
Tafel slopes of anodic curve (a) and cathodic
Fig. 2Polarization curves of mild steel in different compositions
of acetic and formic acid at 35C : () 20% acetic acid + 0%
formic acid, (o) 19% acetic acid + 1% formic acid, () 18%
acetic acid + 2 formic acid and () 15% acetic acid + 5% formic
acid
Table 1Electrochemical parameters of mild steel in different compositions of acetic and formic acid at 25, 35 and 45C.
curve (c) and the corrosion rate calculated from
the polarization curves at different compositions of
formic and acetic acids have been recorded in
Table 1 at 25, 35 and 45C. The equation-Corrosion
rate (mpy) = 0.1288 Icorr E/D, where Icorr is
corrosion current density in A/cm2 , E is equivalent
weight of metal (working electrode), D is density
of metal in g/cm3, was used to calculate the
corrosion rate. The Tafel constant a and c were
obtained from the slopes of the linear anodic
and cathodic curves in this region. The anodic
and cathodic polarization curves were extrapolated
and the projections of their intersection point on
the corresponding axes yielded the values of
Ecorr and Icorr.
It is clear from the data mentioned in the Table 1
that as the composition of formic acid is increased
from 0 to 5% in the mixture the Icorr value gradually
increases indicating an increase in corrosion rate. The
corrosion rates obtained by both the techniques
provide similar conclusions of increasing corrosion
rate with increasing concentration of formic acid in
the mixture.
The temperature of the system has a marked
influence on the corrosion parameters, as given in
Table 1. The values of Icorr have increased enormously
for a ten degree rise in temperature at all compositions
of the electrolyte mixture and consequently a similar
increase in the corrosion rate has also been observed.
An appreciable increase in limiting current is also
noticed.
The plots of log Icorr derived from the anodic
polarization curves at different mixture compositions
of formic and acetic acids against 1/T, where T is

Composition of acetic Icorr Ecorr Anodic Tafel slope Cathodic Tafel slope Corrosion rate
and formic acid (%) (A/cm2) (mV) (a) (mV/decade) (c) (mV/decade) (mpy)
At 25C
20 : 0 151.36 -597 188 217 69.26
19 : 1 169.82 -598 225 220 77.71
18 : 2 213.80 -595 200 230 97.83
15 : 5 263.03 -600 214 227 120.36
At 35C
20 : 0 261.71 -600 217 250 119.76
19 : 1 331.13 -604 200 228 151.52
18 : 2 398.12 -598 197 244 182.17
15 : 5 602.56 -586 225 266 275.73
At 45C
20 : 0 389.19 -625 230 235 178.09
19 : 1 492.04 -600 200 237 225.16
18 : 2 582.10 -600 200 250 266.37
15 : 5 860.99 -600 204 260 393.99
 SINGH et al.: CORROSION BEHAVIOUR OF MILD STEEL IN AQUEOUS ACETIC ACID
the absolute temperature, are shown in Fig. 3. The
linearity of these plots indicates that the reaction
is activation controlled.
The anodic polarization behaviour of mild steel
in the mixture of acetic and formic acids of various
compositions determined at different temperatures
is kinetically similar to the corrosion behaviour
observed from the weight loss measurements.
However, these studies are not sufficient to ascertain
the role of individual acids in the corrosion process.
This necessitated the extension of our polarization
studies to include certain additional experimental
conditions. In this context, studies pertaining to
the effect of various salts on the polarization
behaviour of mild steel were undertaken. For this
purpose three different sodium salts have been
chosen. These are (i) sodium acetate having a
common anion with acetic acid, (ii) sodium formate
having a common anion with formic acid and
(iii) sodium sulphate which does not have any
common ion with either of the two acids.
The effect of the addition of 0.5 M sodium acetate
to different mixtures of acetic and formic acid on
anodic and cathodic polarization behaviour of
mild steel at 35C is illustrated by the curves in Fig. 4.
The most remarkable feature of these curves is the
transition from active to active-passive-transpassive
behaviour in some cases. Further, in the active region
the polarization curves for various compositions
are too closely spaced to distinguish them easily.
Fig. 3Plot of log icorr versus 1/T for various compositions of
acetic and formic acid mixture: () 20% acetic acid + 0% formic
acid, (o) 19% acetic acid + 1% formic acid, () 18% acetic
acid + 2 formic acid and () 15% acetic acid + 5% formic acid
295
The effect of salt addition on the anodic
polarization curves has been found to depend on
the composition of the mixture. In 20% acetic
acid, when there is no formic acid at all, sharp
active-passive-transpassive behaviour has been
observed. The passive potential range observed in
this case has been quite large and it extended
from 300 to 1160 mV. As the specimen was
anodically polarized, the current density at first
increased, attained a maximum value and then
remained constant over the -100 to -60 mV potential
range before decreasing. Thus, the magnitude
of critical current density ic, has been found to
be 40.738 mA and potential for primary passivity
Epp,-100 mV. An abrupt increase in current has been
observed above the potential of 1160 mV, showing
breakdown of passivity.
The presence of 1% formic acid in the mixture
resulted in considerable change in the passive
behaviour. The active-passive transition occurred at
a much higher potential and the passive potential
range was drastically shortened. Further, the passive
current ip, is found to be manifold higher than that
observed in the absence of formic acid. With further
increase in formic acid content in the mixture, the
passive behaviour gradually disappears. From the
slight decrease in current density observed in the
limiting region, after reaching a maximum value at
different potentials for mixtures having 2 and 5%
formic acid, it may be concluded that the electrode
Fig. 4Polarization curves of mild steel for different
compositions of acetic and formic acid mixture in the presence of
0.5M CH3COONa at 35C: () 20% acetic acid + 0% formic acid,
(o) 19% acetic acid + 1% formic acid, () 18% acetic
acid + 2 formic acid and () 15% acetic acid + 5% formic acid
296 INDIAN J. CHEM. TECHNOL., JULY 2011
has a tendency to become passive in mixtures of
these compositions, though none of the relevant
parameters can be precisely defined.
On the basis of the above findings an attempt has
been made to understand the specific roles played by
these acids during corrosion of mild steel in their
mixtures. The very occurrence of passivity in 20%
acetic acid containing 0.5 M sodium acetate has
already been reported earlier45. The observed
passivity was attributed to the formation of an
adherent and non-porous salt film of iron acetate or
basic iron acetate (Fe [OH]2 CH3COO) at higher
anodic potential in the passive range. Thus, in the
present case too, such a film is expected to be
formed as indicated by the extended passive
range and very small passive current density ip. The
gradual disappearance of passive behaviour with
increase in formic acid content seems to be due to
a subsequent decrease in the concentration of
acetic acid. However, well defined active-passive-
transpassive behaviour of mild steel in 5 and 10%
acetic acid containing 0.5M sodium acetate has
already been reported in literature45. This indicates
that the observed behaviour in the presence of formic
acid is not due to the corresponding decrease in
acetic acid concentration but the specific role played
by formic acid.
The nature of the anodic polarization curves in the
mixture containing 19% acetic acid, 1% formic acid
and 0.5M sodium acetate has indicated substantial
loss of passivity, both in terms of decrease in passive
potential range and large increase in ip. It is apparent
from the larger value of current density in the
passive region that the film formed at this
composition is porous in nature. The porosity of the
film must have been caused by the presence of 1%
formic acid in the mixture.
The role of formic acid in disrupting the passivity
can be understood in the light of the mechanisms
proposed earlier for the anodic dissolution of mild
steel in aqueous acetic45 and formic acid46 separately.
The corrosion of mild steel in aqueous acetic acid
solutions has been described to occur in following
stages:
- -
Fe + CH3COO [Fe(CH3COO)] + e
ads
+ -
[Fe(CH3COO)] [Fe(CH3COO)] + e
ads
+ + 2+
[Fe(CH3COO)] + H Fe + CH3COOH
The mechanism of anodic dissolution in formic
acid is written in a similar manner by replacing
acetate ions and acetic acid by formate ions and
formic acid, respectively. In the presence of sodium
acetate, the dissociation of acetic acid is reduced
appreciably and hence sufficient number of H+ is not
available for the last step to proceed in a significant
manner and the salt film remains intact on the surface
leading to passivity. Hydrogen ions added to the
mixture in the form of formic acid initiate the
dissolution of the film leading to porosity. Further,
co-deposition of formate ions along with acetate ions
and subsequent dissolution in accordance with the
above mechanism would leave behind pores in the
passive film. With increase in the formic acid content
in the mixture more and more disruption of passive
film would occur and ultimately the passivity will
completely disappear, as is actually observed.
The anodic polarization behaviour of mild steel in
various mixtures of acetic and formic acids in the
presence of sodium formate is illustrated in Fig. 5. It
is evident from the figure that the effect of formate
ions on the polarization behaviour is different from
that of acetate ions in many ways. Firstly, the
nature of polarization curves does not depend on
the composition of the mixture. Secondly, active
behaviour is observed at all compositions and over
the whole range of potentials. There is no passivity.
Lastly, these curves look like a cluster of points and no
regular shift is observed due to change in composition.
(1)
Fig. 5Polarization curves of mild steel for different
(2) compositions of acetic and formic acid mixture in the presence of
0.5M HCOONa at 35C : () 20% acetic acid + 0% formic acid,
(3)
(o) 19% acetic acid + 1% formic acid, () 18% acetic acid + 2
formic acid and () 15% acetic acid + 5% formic acid
 SINGH et al.: CORROSION BEHAVIOUR OF MILD STEEL IN AQUEOUS ACETIC ACID
These observations indicate that the conductivity
of the solution is very high due to the presence of
0.5M sodium formate and change in conductance
due to compositional variation of the mixture is
negligible. It may be due both to a decrease in the
degree of dissociation of formic acid in the presence
of a high concentration of formate ions and also
the dissociation of acetic acid remaining unaffected.
The shift of polarization curves occurs on both sides
as in the case of pure acids but the shift is almost
negligible due to high conductance of the solution.
The effect of sodium sulphate is quite different
from that observed for sodium formate (Fig. 6). In this
case the curves are distinguishable and the shift in the
polarization curves with increase in the formic acid
content in the mixtures occurs in a manner similar to
that observed in the case of mixtures without any salt.
This is due to the non-interfering nature of the
sulphate ions. Since the conductance of the solution is
very high in the presence of the salt, any change in
conductance of the solution due to presence of formic
acid in different amounts is negligible. Therefore, the
extent of shift in this case is much smaller.
From the cathodic polarization behaviour at 35C
(Fig. 2) it can be noted that the nature of the curves is
independent of the composition of the mixture. The
polarization curve for 20% acetic acid occupies an
extreme left position in the figure. With successive
increase in formic acid content in the mixture, the
curves gradually shift towards region of higher
current density. The shift becomes more and more
pronounced at higher cathodic potentials.
Fig. 6Polarization curves of mild steel for different
compositions of acetic and formic acid mixture in the presence
of 0.5M Na2SO4 at 35C: () 20% acetic acid + 0% formic
acid, (o) 19% acetic acid + 1% formic acid, () 18% acetic
acid + 2 formic acid and () 15% acetic acid + 5% formic acid
297
The increase in the rate of cathodic reaction
as indicated by the shift of cathodic polarization
curves towards higher current density region
with increasing formic acid content in the mixture
can be easily explained in terms of the relative
rates of cathodic reaction in formic and acetic acids.
It has been reported earlier that hydrogen evolution
reaction occurs faster in formic acid46,48 than
in acetic acid45,47 at the mild steel cathode. The
cathodic polarization curves in the present
investigation were similar to those obtained for
aqueous acetic and formic acids and resembled
the hydrogen evolution reaction. The effect of
temperature is also on expected lines.
From the cathodic polarization curves observed
in the presence of 0.5M of each of sodium acetate
(Fig. 4), sodium formate (Fig. 5) and sodium sulphate
(Fig. 6) in the acetic and formic acids, it is apparent
that the nature of curves and their relative shift with
change in composition of the mixture are quite
similar. This indicates that the mechanism of cathodic
process is unaffected by the presence of salts.
Surface study
Microphotographs of mild steel specimens before
and after the completion of anodic polarization studies
and subsequent removal of the corrosion products
were obtained. Figure 7a shows the micrograph of
an uncorroded freshly polished sample. Its surface
is smooth and homogeneous. Polishing streaks are
visible at very high magnifications, viz., 900. Figure
7b shows mild steel specimens exposed in 20% acetic
acid in the absence of any salt. The polishing streaks
were not visible and the uniform nature of mild steel
corrosion was observed with slight unevenness on
the surface. The sample has a gray appearance after
treatment, having lost its metallic colour.
Figures 7(c), (d) and (e) represent mild steel
exposed to 20% acetic acid in the presence of 0.5M
sodium acetate, sodium formate and sodium sulphate
salts, respectively. Comparison of these photographs
reveals that a very limited attack takes place in the
presence of acetate salt. The surface does not appear
corroded in several zones. Presence of some sort of
film is observed on large portions of the surface
which confirms the occurrence of passivity. In these
specimens the corrosion product that was not removed
after treatment adhered to the surface. Thus, a salt
layer present on the surface of the specimen acts as
a barrier at the metal electrolyte interface against
the corrosive medium, consequently resulting in the
298 INDIAN J. CHEM. TECHNOL., JULY 2011

Fig. 7(a) SEM micrograph of uncorroded polished mild steel, 900X, 20 kV, (b) SEM micrograph of mild steel in 20:0 acetic-formic
acid at 35C, 900X, 10KV, (c) SEM micrograph of mild steel in 20:0 acetic-formic acid in presence of 0.5M CH3COONa at 35C,
900X, 10 kV, (d) SEM micrograph of mild steel in 20:0 acetic-formic acid in presence of 0.5M HCOONa at 35C, 900X, 10 kV and
(e) SEM micrograph of mild steel in 20:0 acetic-formic acid in presence of 0.5M Na2SO4 at 35C, 900X, 10 kV
 SINGH et al.: CORROSION BEHAVIOUR OF MILD STEEL IN AQUEOUS ACETIC ACID
retardation of corrosion process. This layer breaks
down in the transpassive region resulting in the
progress of corrosion. No such behaviour was
observed in case of either sodium formate (Fig. 7d) or
sodium sulphate (Fig. 7e). In both these cases the
SEM investigations indicated that corrosion proceeds
via random distributed spots yielding a surface that is
rough and irregular with more unevenness. Increased
potential continued the destruction process which
leads to a loose network of corrosion product on the
surface. This is in conformity with the fact that after
the completion of experiment the corrosion product
could be easily removed with running tap water and
cotton pad.
Conclusions
The following conclusions can be drawn from this
study:
(i) Active anodic polarisation behaviour of mild
steel was observed in formic and acetic acid
mixtures in the absence of salt.
(ii) Corrosion rate in acetic acid increases with
successive increase of formic acid content in
the mixture.
(iii) The temperature has a marked effect on the
corrosion rate of mild steel in acetic-formic
acid mixtures.
(iv) The presence of 0.5M sodium acetate caused
passivation of mild steel when acetic acid is
taken alone and the passivating tendency is
reduced by formic acid.
(v) In case of passive behaviour of mild steel in
acetic acid buffer solutions, the relatively
high anodic current in the active region
suggests that the primary passivating layer is
a non-protective and highly porous salt
layer.
(vi) The addition of sodium formate and sodium
sulphate does not lead to passivity.
References
1 Otero E, Pardo A, Utrilla M V, Perez F J & Merino C,
Corros Sci, 39 (1997) 453.
2 Singh V B & Singh R N, Corros Sci, 37 (1995)1399.
3 Thirumalaikumar M & Jegannathan S, Port Electrochim
Acta, 29 (2011) 1.
4 Quraishi M A & Sharma H K, J Appl Electrochem, 35 (2005)
33.
5 Pasi Kangas, Mark Newman, Anti-Corros Method M, 45
(1998) 233.
299
6 Wagner Jr F S, in KirkOthmer Encyclopedia of Chemical
Technology, 4th ed, vol 1 (John Wiley and Sons), 1991, 121.
7 Augilo A, et al., in Ullmann, s encyclopedia of industrial
chemistry, 5th completely revised edition, vol A1, (V C H
Verlagsgesellschaft), 1985, 45.
8 Teeple H O, Corrosion, 13 (1957) 79.
9 Othmer K (ed), Encyclopedia of Chemical Technology, 3rd
Ed, (Wiley, New York), 1978, 814.
10 Nagarale R K, Gohil G S, Shashi V K, Trivedi G S, Thampy
S K & Rangarajan R, Desalination, 171 (2004) 195.
11 Werner R, Heinz K, in Ullmans Encyclopedia of
industrial chemistry, (Wiley-VCH, Weinheim), 2002, doi:
1002/ 14356007.012 013.
12 Griggs, J P, J Appl Poult Res, 14 (2005) 750.
13 Garcia V, Catala-Gregori, Hemandz P, Megias F & Madrid
M D, J Appl Poult Res, 16 (2007) 555.
14 Taylor K C, Katheeri M I & Nasr-El-Din H A, SPE J,
10 (2005) 152.
15 Lorenzo B F & Kiely P O, Irish J Agri Food Res, 47 (2008) 135.
16 Zaritskii V I D, Chem Pet Eng, 22 (1986) 455.
17 Joo F, Chem Sus Chem, 1 (2008) 805.
18 Invernizzi A J, Sivieri E & Trasatti S P, Mater Sci Eng A,
485 (2008) 234.
19 Monticelli C, Brunoro G, Frignani A & Zucchi F, Mater
Corros, 39 (2004) 379.
20 Jiang Y, Wu Y & Wang K, Mater Corros, 57 (2006) 418.
21 Yihui Ding, Weitluang, Ping Jin & Kechang Xie, Prepr
Pap- Am Chem Soc, Div Fuel Chem, 49 (2004) 57.
22 Vanessa Fajardo, Christian Canto, Bruce Brown & Srdjan
Nesic, Effect of Organic Acids in CO2 Corrosion, Corrosion/
07 (Houston, TX: NACE) 2007, paper no. 07319.
23 Notoya T, Mater Perform, 32 (1993) 53.
24 Amri J, Gulbrandsen E & Nogueira R P, Electrochim Acta,
54 (2009) 7338.
25 Molera P, Sanz-Soro F & Sunol J J, Mater Corros, 57 (2006)
568.
26 Te-Lin Yau, Outlook, 8 (1987) 3.
27 Teeple H O, Corrosion, 8 (1952) 14.
28 Heitz E, in Advances in Corrosion Technology, edited by
Fontana M G & Staehle RW, vol 4, (Plenum Press, New
York), 1974, 149.
29 Xiang Gao, Junlei Tang, Yuzuo & Yuming Tang, Corros Sci,
51 (2009) 1822.
30 Bastidas J M, Chico B, Alonso M P & Mora E M, Mater
Corros, 46 (1995) 515.
31 Bastidas J M & Mora E M, Can Metall Q, 37 (1998) 57.
32 Helene Aubin & Christian Roy, Pet Sci Technol, 8 (1990) 77.
33 Quraishi M A & Ansari F A, J Am Chem Soc, 80 (2003) 705].
34 Nyborg R, Corrosion/ 2002, paper no.02233.
35 Kermani B M & Morshed A, Corrosion, 59 (2004) 659.
36 Groysman A & Erdman N, Corrosion, 56 (2000) 1266.
37 Crolet J L & Bonis M R, The Role of Acetate ions in
CO2 Corrosion, Corrosion/83, paper no,160 (NACE,
Houston,TX), 1983.
38 Otto K, Bartosiewicz L & Carter III R O, Corros Sci, 25
(1985) 117.
39 Goel P, Bhardwaj V, Patil J C, Singhal L K & Mittal I D,
Role of SS Material to Combat Corrosion in Sugar Industry,
Proc 68th Annual Conv STAI, 2007, 84.
40 Goel P, Khosla R, Singhal L K & Goel R K, Inter Sugar J,
CIX (2007) 449.
41 Schaffler K J, Day-Lewis C M J & Montocchio G, Proc 62nd
Annual Congress S Africa Sugar Technol Assoc, 1988, 9.
300 INDIAN J. CHEM. TECHNOL., JULY 2011
42 Asadullah M, Rahman M A, Ali M , Motin M A, Sultan M
B, Alam M R & Rahman M S, Biosource Technol, 99 (2008)
44.
43 Anthony U O & Offiong, U E, Nutritional Quality of
Plant Foods, Post Harvest Research Unit Report, 1998,
Department of Biochemistry, University of Benin, Benin,
Nigeria.
44 Badmos A Y & Ajimotokan H A, The corrosion of mild steel
in orange juice environment, Technical Report No: 2009-02,
Department of Mechanical Engineering, University of Ilorin,
Ilorin, Nigeria, February 2009.
45 Singh M M & Gupta A, Corrosion, 56 (2000) 371.
46 Singh M M & Gupta A, Mater Chem Phys, 46 (1996) 15.
47 Singh S K & Mukherjee A K, J Mater Sci Technol, 26 (2010)
264.
48 Singh S K, Mukherjee A K & Singh M M, Can Metall Q, 50
(2011)186.
49 Singh S K, Mukherjee A K & Singh M M, Indian J Chem
Technol, 15 (2008) 68.
50 Singh S K, Mukherjee A K & Singh M M, Indian J Chem
Technol, 15 (2008) 174.