j m a t e r r e s t e c h n o l .

2 0 1 9;8(1):1366–1378

Available online at www.sciencedirect.com

www.jmrt.com.br

Original Article

Electrochemical investigation on effect of sodium

thiosulfate (Na2 S2 O3 ) and ammonium chloride
(NH4 Cl) on carbon steel corrosion

Prince Kumar Baranwal, Prasanna Venkatesh Rajaraman ∗

Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, India

a r t i c l e i n f o a b s t r a c t

Article history: The effect of sodium thiosulfate (Na2 S2 O3 ) concentrations (0.01, 0.1 and 1 M) on carbon steel
Received 13 January 2018 corrosion behavior in 3.75 M ammonium chloride (NH4 Cl) solution was investigated. The
Accepted 31 May 2018 potentiodynamic polarization results show that the icorr increases from 8.7 × 10−6 A cm−2 to
Available online 28 November 2018 7.2 × 10−4 A cm−2 when thiosulfate (S2 O3 2− ) concentration increases from 0 to 1 M. Electro-
chemical impedance spectroscopy measurements also mimic the same trend. However, it
Keywords: is also observed that the icorr value starts decreasing when S2 O3 2− concentration equals or
Carbon steel exceeds the NH4 Cl concentration (Cl− :S2 O3 2− ≥ 1:1) in the electrolyte solution. The polar-
Ammonium chloride ization behavior and field-emission scanning electron microscopy images reveal that the
Sodium thiosulfate carbon steel undergoes general corrosion at lower concentrations (0.01 M S2 O3 2− and 0.1 M
Electrochemical techniques S2 O3 2− ) and, both pitting and general corrosion at higher concentration (1 M S2 O3 2− ). Based
Corrosion mechanism on the experimental results, the mechanistic reaction pathway, which involves two disso-
lution paths for carbon steel dissolution is suggested.
© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier
Editora Ltda. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

(S2 O3 2− ) has been reported to be a well identified problem in oil

1. Introduction
refinery units, particularly in the sulfurous processing streams
[4–6], in addition to pulp and paper industry [10,11] and
In oil refinery industries, ammonium chloride (NH4 Cl) cor-
nuclear power industry [12]. Of all the sulfur species, S2 O3 2− is
rosion has been reported to be one of the main causes of
found to be one of the most intriguing, metastable polysulfur
equipment and piping failures [1–3]. Severe corrosion fail-
oxyanions, which can undergo both oxidation and reduction
ures result from aggressive species such as chlorides, sulfur,
or disproportionation and decomposition [5,13,14] depending
amines, salts, carbon dioxide and acids present in crude
upon the corresponding electrochemical/chemical environ-
oil [1–9]. Among them, polythionates, especially thiosulfates
ment. Marcus et al. [15] developed potential-pH diagram for Fe
in water containing various sulfur species including S2 O3 2− at
25 ◦ C and 300 ◦ C.
∗
Corresponding author. Besides, S2 O3 2− renders a thermodynamic basis for use as
E-mail: [email protected] (P.V. Rajaraman). a substitute of noxious hydrogen sulfide (H2 S) in laboratory
https://doi.org/10.1016/j.jmrt.2018.05.029
2238-7854/© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier Editora Ltda. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378 1367

scale corrosion studies of sour gas conditions [5,6]. This was diffraction (XRD), field emission scanning electron microscopy
basically proposed based on the following reactions, where the (FESEM) and energy dispersive X-ray spectroscopy (EDS) were
elemental sulfur generated via both electrochemical (Reaction employed to support our research findings.
1) and chemical (Reaction 2) reactions, may further undergo
disproportionation (Reaction 3)/reduction (Reaction 4) to pro-
duce H2 S: 2. Experimental

S2 O3 2− + 6H+ + 4e− → 2S + 3H2 O (1) 2.1. Materials

S2 O3 2− + H+ → S0 + HSO−
3 (2) All the measurements were carried out with carbon steel of
following composition (wt.%): C (0.22–0.26) %; Si (0.11–0.14) %;
4S0 + 4H2 O + H+ → 3H2 S + SO4 2− + 3H+ (3) Mn (1.03–1.06) %; P (0.04% maximum); S (0.03% maximum); Cr
(0.03% maximum); and rest Fe. The electrolytes were prepared
S + 2H+ + 2e− → H2 S (4) utilizing chemicals of analytical reagent grade (NH4 Cl from
Himedia, India; Na2 S2 O3 from Loba Chemie, India) and dis-
Thus, investigating the combined effect of S2 O3 2− and tilled water. The experiments were performed at natural pH of
chloride (Cl− ) ions on corrosion of various metal alloys has the solution: 4.22 for pure 3.75 M (20 wt.%) NH4 Cl solution; 4.54,
been of great interest. The corrosive effect of S2 O3 2− –Cl− ions 5.32 and 6.16 respectively for 3.75 M NH4 Cl solution containing
[10–12,16–23] on various metal alloys have been reported. 0.01 M, 0.1 M and 1 M Na2 S2 O3 respectively. The pH values of
Wensley et al. [10] reported that polysulfides and S2 O3 2− pure 0.01 M, 0.1 M and 1 M Na2 S2 O3 solutions are 6.5, 7.57 and
present in white liquor caused a detrimental effect on mild 8.99 respectively. The microscopy image of carbon steel sam-
steel by degrading the passivating ability of the steel. It was ple was obtained using an optical microscope (Leica DM2500
observed that the sulfur adsorbed on the surface prevented M, Germany), which reveals the presence of ferrite, bainite and
the repassivation process in Cl− solutions. X-ray photoelec- pearlite phases (Figure S1).
tron spectroscopy (XPS) studies [22] showed that sulfate ions
are reduced on the metal electrode (M) surface as per the fol-
2.2. Electrochemical measurements
lowing reactions:

The electrochemical measurements were performed using a

M + S2 O3 2− + H2 O → M-Sad + SO4 2− + 2H+ + 2e− (5)
potentiostat (PGSTAT 204, Switzerland), and a conventional
three electrode system. Ag/AgCl (3 M KCl) was used as the
xM-Sad + (y − x)S → Mx Sy (sulfide) (6)
reference electrode and a Pt wire as the counter electrode.
The working electrode was cylindrical carbon steel of 8 mm
It was reported that Cl− :S2 O3 2− ratio is one of the most
diameter with exposed surface area of 0.5 cm2 to the elec-
significant factors in enhancing pitting corrosion of steels in
trolyte solution. The solution temperature was controlled at
Cl− media. Also, it was found that S2 O3 2− ions are not corro-
(25.5 ± 1) ◦ C. During the experiments, the corrosion cell was
sive enough when present alone, as it does not initiates the
housed inside a faraday cage to minimize the external noises.
breakdown of the passive film formed on the steel surface
Prior to each experiment, the surface of the working elec-
[16,17,19,24]. However, these studies were conducted for other
trode was pretreated by grounding sequentially with 220, 320,
steel alloys and hence, understanding the corrosion mecha-
600 and 1000 grades of silicon carbide (SiC) paper, followed
nism of carbon steel in Cl− –S2 O3 2− system will be of interest
by polishing with 1.0 ␮m and 0.3 ␮m alumina powder. Then,
in the present work.
the electrode was rinsed with distilled water, and ultrasoni-
Similarly, in the studies reported in the literature, NaCl
cated to remove any particle adhered on the specimen surface.
solutions were mainly considered and to the best of author’s
The electrode was finally rinsed and dried using tissue paper.
knowledge, the effect of S2 O3 2− ions in the presence of NH4 Cl
The sample was pretreated to ensure that the results obtained
solution for carbon steel was not investigated yet. Although,
are repeatable and reproducible. All the experiments were
cations will not participate in the electrochemical reactions
performed at least thrice to check the repeatability and repro-
directly, it may alter the anionic activity and, thereby affect
ducibility of the results. On the whole, all the experiments
the corrosion rate and mechanism. Many parameters such as
were carried out in naturally aerated stagnant electrolyte solu-
pH of the electrolyte solution, hydrolysis of cations, hardness
tions.
of cations, corrosion inhibitory effect of cations, formation and
solubility of corrosion products in the presence of given cation
will influence the corrosion rate as well as the mechanism 2.2.1. Polarization measurements
[25–28]. Hence, the investigation of effect of sodium thiosul- The polarization measurements were performed once the
fate (Na2 S2 O3 ) on the corrosion behavior of carbon steel in open circuit potential (OCP) reached a stable value after 1 h
NH4 Cl solution is of particular interest in the present work. (refer Figure S2). Potentiodynamic polarization was employed
The electrochemical techniques such as linear polariza- by sweeping the potential from −250 mV (vs. Ag/AgCl) to
tion, cyclic voltammetry (CV) and electrochemical impedance +500 mV (vs. Ag/AgCl) w.r.t OCP, at a scan rate of 1 mV s−1 .
spectroscopy (EIS) were performed to analyze the corrosion Potentiostatic polarization measurements were also per-
mechanism of carbon steel in NH4 Cl solution containing formed at various overpotentials in order to understand the
S2 O3 2− ions. In addition, other techniques such as X-ray pitting behavior of carbon steel.
1368 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378

2.2.2. Cyclic voltammetry 101

The cyclic voltammogram of carbon steel in different concen-
trations of corrosive media were obtained by sweeping the
10-1
potential linearly from starting potential, −1.20 V (vs. Ag/AgCl)
to −0.20 V (vs. Ag/AgCl) and then reversed back to the start-
ing potential at a potential scan rate of 50 mV s−1 . Scanning 10-3

i / A cm-2
was also performed from −0.20 V (vs. Ag/AgCl) to −1.20 V (vs.
Ag/AgCl) and vice versa, and no significant change in peak 10-5 blank
position and intensity was observed. 0.01 M S2 O3
2-

2-
0.1 M S2 O3
10-7
2.2.3. Electrochemical impedance spectroscopy 1 M S2 O3
2-

Before each experiment, the working electrode (specimen)

surface was exposed to open circuit for a period of 1 h. The 10-9
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2
impedance responses were obtained by employing an ampli-
tude signal of 10 mV (rms) at the corresponding OCP value, E / V vs. Ag/AgCI (3 M KCI)
within the frequency range of 10 kHz to 10 mHz, with 7 fre-
Fig. 1 – Potentiodynamic polarization curves of carbon steel
quencies per decade. The impedance results were further
corroded in 3.75 M NH4 Cl solution containing various
analyzed with electrical equivalent circuit (EEC) model using
concentrations of S2 O3 2− . Scan rate = 1 mV s−1 .
Nova software (Metrohm Autolab, Switzerland). The EIS data
obtained was validated with Kramers Kronig transform in
order to ensure the stability, linearity and causality of the
system. 3. Results and discussion

2.3. Surface analysis using immersion tests 3.1. Potentiodynamic polarization

The surface morphology of carbon steel was inspected via In the current investigation, the NH4 Cl concentration was
field emission scanning electron microscope (FESEM) [Zeiss, fixed at 3.75 M and the concentration of Na2 S2 O3 was varied
Sigma, Germany], in order to confirm the type of corrosion from 0.01 M to 1 M, to understand the combined effect on car-
attack. The steel specimen was immersed in nitric acid (70%, bon steel corrosion. The concentrations used in the study are
as received), and rinsed with distilled water. Further, the usually encountered in the refineries, as reported in the liter-
specimen was polished with SiC paper and abrasive alumina atures [1–3,16,17,19,22,23]. Fig. 1 shows the potentiodynamic
powder. Subsequently, the sample was rinsed with distilled polarization behavior of carbon steel in NH4 Cl solution con-
water, ultrasonicated, dried and then introduced in the respec- taining various concentrations of S2 O3 2− ions. It is to be noted
tive corrosive media for 12 h. At the end of 12 h, the specimen here that the molar ratio of Na2 S2 O3 to NH4 Cl is less than one
was taken out of the system, washed with distilled water and for all the cases. Table 1 shows Ecorr and icorr values, which
dipped in nitric acid to remove the corrosion layer formed were obtained from these polarization curves by means of cor-
on the surface. The steel specimen was then rinsed with dis- rosion fit analysis, using Nova 1.10.4 software. In some cases,
tilled water, air dried and finally, the micrograph images were where the polarization curves do not possess linear range long
taken. enough for extrapolation, estimating Tafel slopes were diffi-
Energy dispersive X-ray spectroscopy (EDS) was performed cult and the reported values might not be accurate. However,
to elucidate the elemental composition of the corrosion prod- the overall trend will not be changed. The polarization curves
ucts using FESEM [Zeiss, Sigma, Germany]. The steel specimen clearly depict a considerable effect of S2 O3 2− on the electro-
was polished in a similar fashion as above, and then sub- chemical behavior of carbon steel in NH4 Cl system. One of
merged in the system of interest for 72 h. the main observations from these polarization curves is that
Ecorr value shifts toward negative potential with the addition
2.4. X-ray diffraction measurement of 0.01 M S2 O3 2− to the NH4 Cl solution. However, the value
of Ecorr keeps increasing to a more positive potential with fur-
X-ray diffraction (XRD) was used to characterize the corro- ther increase in S2 O3 2− concentration. Similar kind of behavior
sion product formed on the carbon steel surface submerged is also reported for carbon steel in caustic soda–thiosulfate
in solutions containing NH4 Cl and Na2 S2 O3 . XRD pat- system [10], and other systems as well [29,30]. On the other
terns were obtained using TTRAX-III (Rigaku) diffractometer hand, the icorr value is increasing from 8.7 × 10−6 A cm−2 to
(Japan), with Cu K␣ ( = 1.5406 Å) radiation (50 kV, 100 mA). 7.2 × 10−4 A cm−2 when the S2 O3 2− concentration increases
The steel specimen was exposed to the respective solu- from 0 M to 1 M. It implies that the addition of S2 O3 2− ions
tion of interest for a period of 72 h, so that sufficient to the NH4 Cl solution accelerates the corrosion rate of carbon
corrosion product is obtained for XRD detection. The cor- steel.
rosion product formed were scrubbed out of the specimen, The substantial increase in the cathodic corrosion current
dried, and placed on a quartz plate to provide a pla- density could also be observed because of the presence of
nar surface in the diffractometer. The XRD pattern was S2 O3 2− ions in the NH4 Cl solution. It would be attributed to
acquired over a range of 10◦ –70◦ , with a scan rate of 4◦ per the role of these species in either of the reduction reaction (1)
minute. or (4) as mentioned in the introductory section. The solution
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378 1369

Table 1 – Ecorr and icorr values attained from potentiodynamic polarization curves.
Electrolyte concentration ˇa (mV dec−1 ) −ˇc (mV dec−1 ) Ecorr (V) icorr (A cm−2 )

Pure 3.75 M NH4 Cl 137.9 62.9 −0.683 8.7 × 10−6

3.75 M NH4 Cl + 0.01 M S2 O3 2− 142.7 362.9 −0.743 1.3 × 10−4
3.75 M NH4 Cl + 0.1 M S2 O3 2− 148.1 375.2 −0.719 3.8 × 10−4
3.75 M NH4 Cl + 1 M S2 O3 2− 160.4 326.4 −0.655 7.2 × 10−4
Pure 0.01 M S2 O3 2− 190.6 159.8 −0.665 2.4 × 10−5
Pure 0.1 M S2 O3 2− 146.5 315.6 −0.743 4.1 × 10−5
Pure 1 M S2 O3 2− 132.2 328.3 −0.789 7.1 × 10−5

pH [31,32], electrochemical potential [14] and nature of the sur- 101

2-
face being corroded (passivated/non-passivated) [12,23,33,34] pure 0.01 M S2 O3

determines the typical cathodic reactions occurring on metal pure 0.1 M S2 O 3

2-

10-1
surface. Besides, the elemental sulfur produced may further pure 1 M S2 O3
2-

react with Fe2+ to form FeS film, thereby accelerating the cor-
rosion process [23]. Similar effect is also reported for NaCl 10-3

i / A cm-2
solution [23], i.e. the addition of Na2 S2 O3 to NaCl solution
influences both the anodic and cathodic reactions. 10-5
It is also interesting to see that the polarization curves
(Fig. 1) show non-linear behavior, which is more evident espe-
10-7
cially at 0.1 M and 1 M Na2 S2 O3 concentrations. In particular,
1 M Na2 S2 O3 solution shows constant current regime, for a
potential range from −0.58 V to −0.45 V (vs. Ag/AgCl), which 10-9
-1.0 -0.8 -0.6 -0.4 -0.2 0.0
indicates the formation of pseudo-passive layer (the current
E / V vs. Ag/AgCI (3 M KCI)
remains more or less constant at 1.1 mA cm−2 ) on the car-
bon steel surface. This layer then finally breaks down at a Fig. 2 – Potentiodynamic polarization curves of carbon steel
breakdown potential (Eb ) of −0.449 V (vs. Ag/AgCl), as evident corroded in various concentrations of pure S2 O3 2−
by the increase of current. The pseudo-passive layer com- solutions. Scan rate = 1 mV s−1 .
prises of a mixture of sulfides and oxides. However, the major
constituent could be sulfides as the formation of the same
is thermodynamically more feasible than the formation of In order to understand further, whether the observed
oxides [34]. behavior at higher Na2 S2 O3 concentrations is due to the pres-
The reduction of S2 O3 2− to sulfur is more likely to happen ence of S2 O3 2− ions alone or because of the combined effect of
on non-passivated surfaces [12,22,34]. In NH4 Cl solutions, the S2 O3 2− and Cl− ions, the polarization experiments were car-
surface is not completely covered with an oxide film, which ried out in pure Na2 S2 O3 solutions (0.01 M–1 M) and the results
triggers the formation of sulfur and thereby FeS layer on the are shown in Fig. 2. For an increase in Na2 S2 O3 concentration,
carbon steel surface. The formation rate of FeS will proba- the curves indicate a marked increase in the current density
bly be increasing with S2 O3 2− concentration, which results in from 2.4 × 10−5 A cm−2 to 7.1 × 10−5 A cm−2 with decrease in
the formation of pseudo-passive layer as evident by the con- Ecorr value from −0.665 V to −0.789 V (vs. Ag/AgCl). The higher
stant current regime in polarization curve. At higher anodic current density in pure S2 O3 2− solutions (2.4 × 10−5 A cm−2 at
potential, the pseudo-passive layer breaks down indicating 0.01 M Na2 S2 O3 vs. 8.7 × 10−6 A cm−2 at 3.75 M NH4 Cl) indi-
the susceptibility of carbon steel to localized corrosion. In cates that S2 O3 2− ions are more aggressive compared to that
general, the sulfide film is more porous and non-protective of Cl− ions in corroding carbon steel surface. Besides, it does
comparing to that of oxide film [34]. Thus, this pseudo-passive not show constant current regime for long potential range as
layer could not completely protect the underlying metal, and observed in case of 1 M S2 O3 2− in 3.75 M NH4 Cl solution (Fig. 1).
as a result, general corrosion also occurs simultaneously at However, a non-linear behavior is observed in the curve at 1 M
higher Na2 S2 O3 concentration. Simultaneous occurrence of S2 O3 2− concentration, which may be due to the formation of
general and pitting corrosion in acidic and neutral solution a porous and non-protective sulfide layer on the surface. This
is also reported for other metals [35,36]. However, at lower implies that susceptibility to pitting enhances only in pres-
Na2 S2 O3 concentrations, the corrosion is of only general type ence of both Cl− and S2 O3 2− species. Thus, when the solution
as observed in the case of pure NH4 Cl solutions [37]. contains only NH4 Cl or Na2 S2 O3 , carbon steel undergoes gen-
As the Na2 S2 O3 concentration varies from 0.01 M to 1 M, the eral corrosion, whereas when the solution contains both the
pH value increases from 4.54 to 6.16. According to Pourbaix species, then carbon steel undergoes either general or pitting
diagram, the passivation due to Fe1+X S/FeS is thermodynam- corrosion depending on the concentration of both the species.
ically feasible in this pH range of 4–8 [15,38,39]. However, the The polarization experiments were further carried out at
pseudo-passive layer is formed only at higher concentration of different molar ratios of Na2 S2 O3 to NH4 Cl: <1, 1 and >1 and
Na2 S2 O3 . Thus, these results clearly depict that concentration the results are shown in Fig. 3. The pH of the corresponding
of Na2 S2 O3 plays a significant role in determining the nature solutions varied from 6.17 to 7.13. It is to be noted that the con-
of the corrosion process. centration of NH4 Cl is fixed at 0.93 M (5 wt.%) instead of 3.75 M,
1370 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378

101 1.0x10-2
1:0.13
(a)
1:0.26
1:0.53 8.0x10-3 (b)
10-1 1:1
1:1.33
6.0x10-3

i / A cm-2
i / A cm-2

10-3
4.0x10-3

10-5 2.0x10-3

0.0
10-7 0 400 800 1200 1600 2000
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 Time / s
E / V vs. Ag/AgCI (3 M KCI)
Fig. 5 – Potentiostatic measurements of carbon steel in
Fig. 3 – Potentiodynamic polarization curves of carbon steel 3.75 M NH4 Cl solution containing 1 M S2 O3 2− at
corrosion in various Cl− to S2 O3 2− concentration. Scan overpotentials: (a) 50 mV below pitting potential (Eb ):
rate = 1 mV s−1 . −0.499 V (vs. Ag/AgCl), and (b) 50 mV above pitting
potential (Eb ): −0.399 V (vs. Ag/AgCl).

and the concentration of Na2 S2 O3 is varied to get these desired

ratios. At 3.75 M NH4 Cl, achieving ratio 1 and >1 is difficult as behavior at two different overpotentials: (a) 50 mV below Eb ,
the solution is saturated. It appears from these results that and (b) 50 mV above Eb . The results obtained are shown in
initially the corrosion rate of the carbon steel in NH4 Cl solu- Fig. 5. When the overpotential is below the pitting potential,
tion increases markedly to a maximum on addition of Na2 S2 O3 the current is constant (1.2 × 10−4 A cm−2 ) with time, which
(as observed in 3.75 M NH4 Cl solution, Fig. 1) and then starts implies that there is no formation of passive layer on the
decreasing when the ratio of Cl− and S2 O3 2− species becomes electrode surface. However, when the overpotential is above
1:1 or higher than 1 as shown in Fig. 4. the pitting potential, the current decreases and then increases
The reason for icorr showing a maxima at particular S2 O3 2− sharply to 9 × 10−3 A cm−2 indicating the growth of pit with
concentration could be explained as follows: In pure NH4 Cl time. After 1600 s, the current value does not increase sig-
solution, the surface coverage of oxide layer is very low [37]. nificantly (saturates at 9.3 × 10−3 A cm−2 ), which implies that
Na2 S2 O3 , being an oxidizer, increases the oxidation state of the growth of pit is impeded by the deposition of corrosion
the carbon steel when added to NH4 Cl solution and thereby products inside the pit.
increases the dissolution rate at lower concentrations. How-
ever, higher concentrations of S2 O3 2− leads to the formation of 3.3. Cyclic voltammetry
thick layer of FeS on the carbon steel surface, which restricts
the Cl− ions or O2 molecules to diffuse through it, and thereby Fig. 6(a)–(d) shows the cyclic voltammograms obtained for
finally lowers the dissolution rate. Thus, both Cl− and S2 O3 2− carbon steel in NH4 Cl media containing S2 O3 2− of varied con-
has a pronounced effect on the corrosion mechanism. centrations. The voltammograms are interpreted in terms of
Fe as the content of other elements in carbon steel is very
3.2. Potentiostatic experiments low. In pure 3.75 M NH4 Cl solution, two anodic peaks A1 and
A2 appeared at −0.581 V and −0.393 V (vs. Ag/AgCl) respec-
The potentiostatic experiments were also carried out for tively. The peak A1 corresponds to oxidation of Fe to Fe2+
carbon steel in the electrolyte solution containing 3.75 M and the peak A2 corresponds to oxidation of Fe2+ to Fe3+ .
NH4 Cl and 1 M Na2 S2 O3 in order to understand the pitting Besides, the high anodic current (A4) is observed at higher

-0.70 4x10-4
Ecorr / V vs. Ag/AgCI (3 M KCI)

a b

-0.72 3x10-4
icorr / A cm-2

-0.74 2x10-4

-0.76 1x10-4
0.0 0.3 0.6 0.9 1.2 1.5 0.0 0.3 0.6 0.9 1.2 1.5

Concentration of S2O32- / M Concentration of S2O32- / M

Fig. 4 – Ecorr and icorr values acquired for various ratio of Cl− :S2 O3 2− .
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378 1371

0.14 0.25
a A4 b A4
0.10 0.18

0.06 A2 0.11
i / A cm-2

i / A cm-2
A1
0.02 0.04 A1 A3

-0.02 -0.03 C2
C1 C1

-0.06 -0.10
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2
E / V vs. Ag/AgCI (3 M KCI) E / V vs. Ag/AgCI (3 M KCI)

0.25 0.20

c A4
d
A4
0.18 0.14
i / A cm-2

i / A cm-2
0.11 0.08

A2
0.04 0.02
A1

-0.03 -0.04
C2 C2
C1 C1

-0.10 -0.10
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2

E / V vs. Ag/AgCI (3 M KCI) E / V vs. Ag/AgCI (3 M KCI)

Fig. 6 – Cyclic voltammograms for carbon steel immersed in: (a) pure 3.75 M NH4 Cl, (b) 3.75 M NH4 Cl + 0.01 M S2 O3 2−
solution, (c) 3.75 M NH4 Cl + 0.1 M S2 O3 2− solution, and (d) 3.75 M NH4 Cl + 1 M S2 O3 2− . Scan rate = 50 mV s−1 .

anodic potentials for all the cases, which is due to the com- However, in NH4 Cl solution containing 1 M S2 O3 2− , there
bined effect of transpassive dissolution and oxygen evolution. appears a region of lower and constant current density from
In the cathodic side, one peak C1 appears at −0.991 V (vs. −0.83 V to −0.65 V (vs. Ag/AgCl), with the disappearance of
Ag/AgCl) which is more likely to be the conjugate peak of A1 peak. The peak A2, which is arising at a comparatively
A1. The peak intensity of C1 for all the cases comes out higher overpotential, −0.466 V (vs. Ag/AgCl) corresponds to
to be slightly more than its counter peak A1, which sug- oxidation of both oxides and sulfides. This suggests that a
gests that most of the species being oxidized are completely pseudo-passive layer is formed on the entire surface. This also
reduced. corroborates with the results obtained from the polarization
On addition of 0.01 M Na2 S2 O3 to the NH4 Cl solution, the measurements (Fig. 1) where formation (insignificant increase
peak A1 shifts toward more negative potential to −0.644 V (vs. in current density) and breakdown of passive layer (significant
Ag/AgCl) and one more peak A3 appears close to A1 peak increase in current density) is observed on the steel surface.
at −0.586 V (vs. Ag/AgCl), which may be due to competitive The occurrence of positive hysteresis in the CV also indicates
diffusion/adsorption of both Cl− and S2 O3 2− ions on the sur- the possibility of pitting corrosion on carbon steel surface.
face. The peak A3 is more likely to be the oxidation of Fe to
form FeS on the electrode surface along with Fe oxide/chloride
layer. Thus, both reactions occur simultaneously on the elec- 3.4. Electrochemical impedance spectroscopy
trode surface. In the cathodic region, in addition to C1, one
more peak C2 appears at −0.759 V (vs. Ag/AgCl), which is The impedance spectra obtained for various concentration of
more likely to be the conjugate peak of A3, i.e. the reduc- S2 O3 2− in NH4 Cl solution are shown in Fig. 7(a)–(c). Although
tion of FeS. Thus, the electrode surface might be covered two time constants (capacitance loops) were observed for all
with mixture of oxide and sulfide layers. When the concen- the cases, the two time constants were not clearly distinguish-
tration of S2 O3 2− in NH4 Cl solution is increased to 0.1 M, the able in some cases, as it is merged together. The electrical
two peaks A1 and A3 merge together, and form as one broad equivalent circuit (EEC) showed in Fig. 7(d) is employed to ana-
peak A1 that appears at −0.653 V (vs. Ag/AgCl). It is indicat- lyze the impedance data quantitatively. Here, Rs represents
ing the increase in aggressiveness of the system due to the the solution resistance, Q1 and R1 corresponds to constant
S2 O3 2− ions. The peak A2 is not observed for these two cases, phase element (CPE) associated with electrical double layer
which may be due to the reason that, the generation of Fe3+ and charge transfer resistance respectively. The other param-
is overshadowed by transpassive and oxygen evolution reac- eters Q2 and R2 corresponds to capacitance and resistance
tions. associated with reduction reactions respectively, while Q3 and
1372 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378

a b
80 100
2.0 blank blank
2- 2-
0.01 M S2 O3 0.01 M S2 O3
1.5
2- 2-
0.1 M S2 O3 0.1 M S2 O3
60 1.0
75
2- 2-
1 M S2 O3 1 M S2 O3
-ZIm / Ω cm2

ZIm / Ω cm2
0.5

40 0.0
0.0 0.5 1.0 1.5 2.0
50

20 25

0 0
0 20 40 60 80 10-3 10-1 101 103 105
ZRE / Ω cm2 log (f / Hz)

c
80
d
blank
2-
0.01 M S2 O3
Q1
2-
60 0.1 M S2 O3
2-
1 M S2 O3
RS
-Phase / º

Q2 Q3 C
40

20 R1

R2 R3

0
10-3 10-1 101 103 105
log (f / Hz)

Fig. 7 – EIS data obtained from carbon steel corrosion in 3.75 M NH4 Cl solution for varied concentrations of S2 O3 2− (a)
Nyquist plot, (b) Bode modulus plot and (c) Bode phase plot; continuous line indicates the EEC fitting of corresponding
impedance data. (d) Equivalent circuit used to fit the EIS data.

Table 2 – Best fit EEC parameters obtained for carbon steel dissolution in different corrosive media; the values within
bracket indicates the error %.
EEC parameters 3.75 M NH4 Cl 3.75 M NH4 Cl + 0.01 M S2 O3 2− 3.75 M NH4 Cl + 0.1 M S2 O3 2− 3.75 M NH4 Cl + 1 M S2 O3 2−

Rs ( cm2 ) 0.8 (1%) 0.7 (1.5%) 0.8 (1.1%) 0.9 (1%)

Q1 –Y10 (−1 cm−2 sn ) 4.7 × 10−4 (3.6%) 1.1 × 10−2 (2.2%) 1.2 × 10−2 (2.3%) 1.4 × 10−2 (3.3%)
Q1 –n1 0.8 (0.5%) 0.85 (0.6%) 0.85 (0.6%) 0.86 (0.9%)
Cdl (F cm−2 ) 6.4 × 10−5 5 × 10−3 5.1 × 10−3 6.6 × 10−3
R1 ( cm2 ) 10 (1.1%) 5.5 (1.9%) 4.3 (1.3%) 3.7 (1.7%)
Q2 –Y02 (−1 cm−2 sn ) 7.5 × 10−2 (1.3%) 7.7 × 10−2 1.4 × 10−1 (1.3%) 1.6 × 10−1 (2.4%)
Q2 –n2 0.6 (0.6%) 0.6 (1.5%) 0.68 (0.8%) 0.65 (1.5%)
R2 ( cm2 ) 778.7 (3.8%) 321.5 (1.8%) 221 (2.2%) 153.2 (1%)
Q3 –Y03 (−1 cm−2 sn ) 2.4 × 10−2 (2.9%) 5.1 × 10−2 (4%) 5.4 × 10−2 (3%) 5.5 × 10−2 (2.1%)
Q3 –n3 0.51 (1%) 0.52 (1.6%) 0.51 (0.9%) 0.54 (0.7%)
R3 ( cm2 ) 18.6 (1.1%) 14.8 (1.5%) 7.5 (1.2%) 7 (1%)

R3 is associated with diffusion phenomenon and chemical behavior [40–44]. The electrical double layer capacitance is
reactions occurring in bulk solution respectively. The EEC calculated from the CPE element using the following Brug’s
parameters obtained are shown in Table 2. It is clearly evident equation and the values are shown in the same Table 2.
that Q1 is increasing and R1 is decreasing with increase in the
S2 O3 2− concentration. Thus, the total impedance associated
with Faradaic reaction decreases as the Na2 S2 O3 concentra-
tion increases. Instead of capacitor, CPE is employed in EEC   n−1 1/n
1 1
model to quantify the non-idealities observed in the capacitor Cdl = Y0 + (7)
Rs Rct
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378 1373

where Cdl is the double layer capacitance, Y0 and n are the CPE are higher, which is attacked further by Cl− ions resulting in
parameters, Rs and Rct are the solution resistance and charge localized corrosion.
transfer resistance respectively. The values of Cdl obtained Fig. 9(a)–(d) shows the results obtained from EDS analy-
for the present system are high. However, similar values were sis, carried out on corrosion products formed on carbon steel
reported for carbon steel in H2 S environment [44,45] and for surface, at different concentrations of S2 O3 2− in 3.75 M NH4 Cl
other systems as well [46–48]. The other capacitive element solution. In pure NH4 Cl solutions, the corrosion film is mainly
Q2 is increasing, while the resistance R2 is decreasing with oxides and chlorides of Fe. When Na2 S2 O3 is added to the
increase in S2 O3 2− concentration. It indicates the fact that the NH4 Cl solution, the sulfur peak appears indicating the for-
cathodic reaction rate increases with S2 O3 2− concentration. mation of sulfide layer on the surface. Thus, the corrosion
The capacitance values are higher compared to Cdl . It might products are oxides and chlorides of Fe in Cl− only solution
be attributed to the adsorption of various corrosion products and a mixture of oxides, chlorides and sulfides in Cl− –S2 O3 2−
on the carbon steel surface [44]. The exponent value of Q3 solutions. EDS analysis were also carried out on the corrosion
is nearly 0.5 in all these cases, which signifies the diffusion product formed inside the pit. The result confirms the pres-
effect. The total impedance arising from these parameters ence of both sulfur and chlorine in the pit (Figure S3). EDS
is decreasing with S2 O3 2− concentration. This indicates that mapping of carbon steel after reaction with 3.75 M NH4 Cl–1 M
the corrosion rate increases with S2 O3 2− concentration as Na2 S2 O3 is also presented in Fig. 10(a)–(d). The result shows
observed in the polarization measurements. that the species S, Cl and O are present on the carbon steel
surface as well as on the pit. These results imply that both sul-
fur and chlorine species took part in the formation of stable
3.5. FESEM and EDS pits as reported by other researchers [12,34]. Also, the species
S and O are more concentrated inside the pit. It indicates that
The surface morphology of carbon steel after immersion in the pits are covered with corrosion products as observed in
NH4 Cl solution containing S2 O3 2− of various concentrations the potentiostatic measurements.
are shown in Fig. 8(a)–(c). As expected from the polariza-
tion behavior, uniform corrosion is observed at lower S2 O3 2− 3.6. XRD
concentrations (0.01 M and 0.1 M), as observed in pure NH4 Cl
solution [37]. While pits are clearly observed at higher S2 O3 2− The crystalline phases of corrosion film formed on carbon
concentration (1 M). It supports our observation from polar- steel surface in NH4 Cl–Na2 S2 O3 solutions were identified by
ization measurements that a pseudo-passive layer is formed XRD spectra and the results are presented in Fig. 11. The
when the concentration of Cl− and S2 O3 2− ions in solution peaks were identified using JCPDS software. XRD spectra

Fig. 8 – FESEM micrographs of carbon steel after immersion in: (a) 3.75 M NH4 Cl + 0.01 M S2 O3 2− solution, (b) 3.75 M
NH4 Cl + 0.1 M S2 O3 2− solution, and (c) 3.75 M NH4 Cl + 1 M S2 O3 2− solution, for a period of 12 h; Square indicates the pit
formed on the surface.
1374 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378

Fig. 9 – EDS analysis of corrosion products formed on the surface of carbon steel after immersion in: (a) pure 3.75 M NH4 Cl,
(b) 3.75 M NH4 Cl + 0.01 M S2 O3 2− solution, (c) 3.75 M NH4 Cl + 0.1 M S2 O3 2− solution, and (d) 3.75 M NH4 Cl + 1 M S2 O3 2−
solution, for a period of 72 h.

exhibits various crystalline phases including ␣-FeOOH, FeCl3 , non-deaerated solution containing dissolved oxygen or dur-
FeS, Fe2 O3 depending upon the concentration of S2 O3 2− in ing its exposure to atmospheric air. The appearance of FeS
NH4 Cl solution. The peaks corresponding to FeS did not appear peaks in the recorded XRD spectra for NH4 Cl–S2 O3 2− solu-
in pure NH4 Cl solution as expected and the corrosion film tions clearly depicts the formation of FeS layer on the carbon
comprises of only FeOOH, FeCl3 and Fe2 O3 . Although, the dis- steel surface. This is also corroborating our results obtained
solution of carbon steel in NH4 Cl solution occurs via Fe2+ , from other techniques employed in the present investiga-
the oxidation of these products to Fe3+ is more common in tion.
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378 1375

a b

5μm Fe Kα1 5μm O Kα1

c d

5μm S Kα1 5μm CI Kα1

Fig. 10 – EDS mapping of carbon steel exposed to 3.75 M NH4 Cl + 1 M S2 O3 2− solutions for a period of 72 h.

Point defect model (PDM) is widely employed to explain the

3.75 M NH4 CI +1 M S2 O32-
+/-/& pitting corrosion of metal alloys [53,54]. As PDM could be
+/- +/- * applied only when strong passive film is present on the carbon
+
steel surface, the following mechanistic reaction pathway is
* +*
+ * +/-/& * suggested to explain the features observed in electrochemical
+
and non-electrochemical experiments.
3.75 M NH4 CI + 0.1 M S2 O32- The following anodic reaction occurs in NH4 Cl solution
+/-
+/- +/-/& (corresponds to peak A1 in CV).
+

Fe → Fe2+ + 2e−
Intensity / a.u.

+ +/-/& + +/-/& sol

(8)
* * + *
3.75 M NH4 CI + 0.01 M S2 O32- Besides, the following chemical reactions also occur in NH4 Cl
+/-
+/-/& solution.
+/-
+

+ + +/-/& NH4 Cl  NH4 + + Cl− (9)

+/-/&
* * + *
Fe2+ + 2Cl−  FeCl2 (10)
+/- 3.75 M NH4 CI

+/- +/-/& FeCl2 + H2 O  FeO + HCl (11)

+
+ + +
+ +/-/& +/-/& The dissolution–precipitation reactions in presence of S2 O3 2−
ions (corresponds to peak A3 in CV) are given by the following
anodic reaction.
10 20 30 40 50 60 70
2θ/º
2Fe + 2H2 S → 2Fe2+ + 2H2 S + 4e− (12)
Fig. 11 – XRD pattern of corrosion products obtained after
carbon steel corroded in 3.75 M NH4 Cl solution containing Fe2+ + H2 S  FeS + 2H+ (13)
S2 O3 2− of varied concentrations. Peak label indicates: +,
(FeOOH); −, (FeCl3 ); *, (FeS); &, (Fe2 O3 ). In the above dissolution reaction, H2 S is regenerated and fur-
ther reacts with Fe2+ to form FeS.
The possible cathodic reactions occurring in the system
are,
3.7. Dissolution mechanism of carbon steel in
S2 O3 2− –Cl− solutions 1 3
S2 O3 2− + 3H+ + 2e−  S + H2 O (14)
2 2
The pitting corrosion is reported for various metal alloys in Cl−
only solutions [12,49–51] and Cl− –S2 O3 2− solutions [12,16,52]. 4H+ + 2S + 2e−  2H2 S (15)
1376 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378

Fig. 12 – The reaction network of carbon steel dissolution in NH4 Cl–Na2 S2 O3 solutions.

O2 + 4H+ + 4e−  H2 O (16) the carbon steel surface is a mixture of oxides, chlorides and
sulfides as evident from EDS and XRD results. Also, CV results
confirm that the redox reactions due to both S2 O3 2− and Cl−
The peaks corresponding to the above cathodic reactions
ions are occurring on the carbon steel surface, unlike in pure
were not observed in CV. It is probably because these reactions
NH4 Cl solutions.
were buried under the other major reduction process of iron
The FeS/FeO/FeCl2 could also undergo partial oxidation
oxides and sulfides. The overall reaction network is presented
(corresponds to peak A2 in CV) as per the following equation
in Fig. 12.
[32,34].
In case of carbon steel in NH4 Cl solution, the corrosion layer
does not completely block the carbon steel surface as observed
FeS + 2H2 O  FeOOH + S2− + 3H+ + e− (17)
from polarization measurement. Consequently, general corro-
sion occurs as reported in our earlier studies [37]. Thus, based
2FeS + 3H2 O  Fe2 O3 + 2S2− + 6H+ + 2e− (18)
upon these results, it could be envisaged that in Cl− only solu-
tions, an oxide-chloride layer could be formed on the carbon
steel surface but not as a continuous layer as shown in Fig. 13a. 2FeO + H2 O  Fe2 O3 + 2H+ + 2e− (19)
With the addition of lower concentrations of S2 O3 2− , FeS
could be precipitated on the carbon steel surface without FeCl2 + Cl−  FeCl3 + e− (20)
blocking the surface layer completely as shown in Fig. 13b.
As the S2 O3 2− addition enhances the dissolution rate also, the Further, these iron oxides dissolved in the solution via
formation of FeS would enhance the anodic reaction rate by transpassive reaction along with oxygen evolution (corre-
acting as a reduction site [23,34]. Further, the pseudo-passive sponds to peak A4 in CV).
layer forms on the carbon steel surface only in the presence Thus, the dissolution of Fe in Cl− –S2 O3 2− solution occurs
of both S2 O3 2− and Cl− ions, especially at higher concentra- via two paths as shown in Fig. 12. As observed from polar-
tions. This implies that the pseudo-passive layer formed on ization measurements, the corrosion rate in pure Na2 S2 O3 is

a b

FeO/ FeCl2 FeS FeO/ FeCl2

Carbon steel Carbon steel

FeO/ FeCl2 FeS Pseudo-passive Pit

layer

Carbon steel Carbon steel

Fig. 13 – Schematic representation of dissolution mechanism of carbon steel in: (a) pure NH4 Cl solution, (b) NH4 Cl solution
containing lower concentration of S2 O3 2− , and (c) NH4 Cl solution containing 1 M S2 O3 2− ; *, ,̂ #, † indicates species O2 , Cl− ,
H2 O and S2 O3 2− , respectively.
 j m a t e r r e s t e c h n o l . 2 0 1 9;8(1):1366–1378 1377

more comparing to the corrosion rate in pure NH4 Cl solutions.

Thus, the dissolution rate via path B would be higher. Besides,
Appendix A. Supplementary data
the concentration of these individual ions would also play
a critical role in determining the nature and the rate of the Supplementary data associated with this article can be found,
process occurring at metal-electrolyte solution interface. For in the online version, at doi:10.1016/j.jmrt.2018.05.029.
example, when the concentration of the S2 O3 2− is increased
to 1 M (the ratio of S2 O3 2− to Cl− is still less than one), the references
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